TW201201384A - Wavelength conversion type photovoltaic cell encapsulating material, and photovoltaic cell module - Google Patents

Wavelength conversion type photovoltaic cell encapsulating material, and photovoltaic cell module Download PDF

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TW201201384A
TW201201384A TW100118278A TW100118278A TW201201384A TW 201201384 A TW201201384 A TW 201201384A TW 100118278 A TW100118278 A TW 100118278A TW 100118278 A TW100118278 A TW 100118278A TW 201201384 A TW201201384 A TW 201201384A
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photovoltaic cell
wavelength conversion
acrylate
conversion type
encapsulating
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TW100118278A
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TWI542024B (en
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Taku Sawaki
Kaoru Okaniwa
Takeshi Yamashita
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0232—Optical elements or arrangements associated with the device
    • H01L31/02322—Optical elements or arrangements associated with the device comprising luminescent members, e.g. fluorescent sheets upon the device
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0617—Polyalkenes
    • C09K2200/062—Polyethylene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06—Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615—Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0622—Polyvinylalcohols, polyvinylacetates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/52—PV systems with concentrators

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electromagnetism (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Photovoltaic Devices (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)

Abstract

A wavelength conversion type photovoltaic cell encapsulating material of the present invention has a first encapsulating layer which does not include a fluorescent material, and a second encapsulating layer which includes a fluorescent material. The wavelength conversion type photovoltaic cell encapsulating material is used as one light transparent layer in a photovoltaic cell module, and is provided on the side of incident surface of a photovoltaic cell.

Description

201201384 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種波長轉換型光電電池封震材料、 以及使用該封裝材料的光電電池模組。更詳細而言，本發 明是有關於一種可藉由使用螢光物質（亦稱為發^材料/， 將對發電無幫助的波長£域的光進行波長轉換為有助於發 電的波長區域的光，而提高發電效率的光電電池模組中使 用的波長轉換型光電電池封裝材料以及光電電池模組。 【先前技術】 先前的矽結晶系光電電池模組為如下所述的構成。表 面的保護玻璃（亦稱為覆蓋玻璃）是注重耐衝擊性而使用 強化玻璃，為了使與封裝材料（通常是以乙烯—乙酸乙烯酯 共聚物作為主成分的樹脂，亦稱作填充物質）的密著性良 好，而對單面施予藉由壓印加工的凹凸式樣。 另外，上述凹凸式樣形成於内侧，光電電池模組的表 面平滑。此外，亦有為了提高太陽光的導入效率，而對外 側，施予凹凸形狀的情況。另外，於保護玻璃的下側設置 有光電電池單元、用以將標記祕護封裝的封裝材料以及 背膜。 例如，日本專利特開2000-328053號公報等提出有多 種如下方法：將藉由❹螢光物質，使太陽光光譜中對發 電的幫助> 的紫外區域或者紅外區域的光進行波長轉換， 而發出對發電的幫助大的波長ϋ域的光的層設置於光電電 池受光面側。 201201384 似專利特開2〇06,3033號公報中提出有使 =:，錯合物作為波長轉換材料而包含於 前出的日本專利特開2〇〇6_3〇3〇33號 域的光進行波長轉丄= 法中’於波長轉換層中含有螢 無機榮光體等另η光體、有機金屬錯合物、 轉換3的_製作包含具有充分的波長 ==二的τ才料，則榮光物質的含量變 【發=】免成本未必適合於工業利用。 模組=持於在應用於光電電池 電池封裝材料。 且仏廉的波長轉換型光電 果發現，螢光解ΐ上述課題而進行積極研究，結 射的太陽光的比例（發電效發電的電力相對於所入 或者其以上的發電效ί 膜厚較厚的情況同等 電電池模組的受光側的若將波長轉換型光 及不含登光物質的層此兩層來形201201384 VI. Description of the Invention: [Technical Field] The present invention relates to a wavelength conversion type photovoltaic cell sealing material and a photovoltaic cell module using the same. More specifically, the present invention relates to a wavelength region in which wavelengths of wavelengths in a wavelength range that contribute to power generation can be wavelength-converted by using a fluorescent substance (also referred to as a material/. The wavelength conversion type photovoltaic cell encapsulating material and the photovoltaic cell module used in the photovoltaic cell module for improving the power generation efficiency. [Prior Art] The prior 矽-crystalline photovoltaic cell module has the following structure. Glass (also known as cover glass) is a tempered glass that emphasizes impact resistance and is used for adhesion to a packaging material (usually a resin containing a vinyl-vinyl acetate copolymer as a main component, also referred to as a filler). In addition, the uneven pattern is applied to the single surface by the embossing process. The uneven pattern is formed on the inner side, and the surface of the photovoltaic cell module is smooth. In addition, in order to improve the introduction efficiency of sunlight, the outer side is also provided. a case where a concave-convex shape is applied. Further, a photovoltaic cell unit, an encapsulating material for encapsulating the enveloping encapsulation, and the like are provided on the lower side of the cover glass. For example, Japanese Laid-Open Patent Publication No. 2000-328053, etc., proposes a method of performing wavelengths in the ultraviolet region or the infrared region of the solar light spectrum by the fluorescene substance in the solar spectrum. In the conversion, the layer that emits light in the wavelength range of the photovoltaic cell is provided on the light-receiving surface side of the photovoltaic cell. 201201384 It is proposed in the Japanese Patent Publication No. 2,06,3033 that the compound is converted to wavelength conversion. The light contained in the field of the Japanese Patent Laid-Open No. 2〇〇6_3〇3〇33, which is included in the material, is wavelength-transformed = in the method of 'in the wavelength conversion layer, which contains another η-light body such as a fluorescent inorganic glaze, and an organic metal error. The composition of the compound 3 and the conversion 3 includes a τ material having a sufficient wavelength == two, and the content of the glory material is changed. The cost is not necessarily suitable for industrial use. Module = is used in photovoltaic cells Packaging materials. The inexpensive wavelength-converting photoelectric fruit has been found to be actively researched by the above problems, and the proportion of sunlight emitted by the power generation (power generation power generation is more effective than the power generation or the above). The film thickness of the light-receiving side is thick if the equivalent electrical battery module light and the wavelength conversion-type light-free landings this substance to form layers

S 201201384 發電效率’而且可實現抵成本化。 即，本發明如下所述。 〈1〉一種波長轉換型光電電池封装材料，包括不含 光物質的第一封裝層以及含有螢光物質的第二封裝層。 〈2&gt;如上述〈1〉所述之波長轉換型光電電池封裝 料’其中上述螢光物質為鏑錯合物。 〈3〉如上述〈1〉或〈2〉所述之波長轉換型光電電、、也 封裝材料，其中上述螢光物質内包於以乙烯基化合物作兔 單體化合物的樹脂粒子中。 ‘'“ 〈4〉一種光電電池模組，包括光電電池單元以及 設置於上述光電電池單元的受光面側的如上述〈丨〉〜 〈3&gt;中任一項所述之波長轉換型光電電池封裝材料。 [發明的效果] 依，本發明，可提供一種在應用於光電電池模組時維 持或提高發電效率，而且價賴波長轉換型光電電池封裝 材料。 ^ 為讓本發明之上述和其他目的、特徵和優點能更 ^下Γ域舉較佳實施例，並配合_圖式，作詳細說 【實施方式】 透光m電電池模組至少包括光電電池單元、作為 型光電電池封裝材料（波長轉換型光電電池 發明中’波長轉換型先電電池封裝材料(以;裝片有= 201201384 含況)是將不含螢光物質的第-封裝層與 ==第:封裝層積層而成。此外，不含榮光物 封裝層觀點而言’含有侧的第二 卜的q成與先前的封裝材料相比製造成j到二 電池封述的兩層結構的波長轉換型光電 維持，。其原因並不明確’但以:發電效率亦 右對光電電池模組射入光，則％ 材料中所含有的$光物質吸收光。此4 r:侧的封裝 ，吸技隨著㈣裝材料_4^#^^= 此，即便使封裝材料的膜厚變厚， ^ 分存在的螢光物質被料方向較深的部 事實上轉換的幫助少的材料。S 201201384 Power generation efficiency can be achieved. That is, the present invention is as follows. <1> A wavelength conversion type photovoltaic cell encapsulating material comprising a first encapsulating layer containing no light substance and a second encapsulating layer containing a fluorescent substance. <2> The wavelength conversion type photovoltaic cell encapsulant as described in <1> above, wherein the fluorescent substance is a ruthenium complex. <3> The wavelength conversion type photovoltaic device according to the above <1> or <2>, wherein the fluorescent material is contained in a resin particle containing a vinyl compound as a rabbit monomer compound. A solar cell module, comprising a photovoltaic cell, and a wavelength conversion type photovoltaic cell package according to any one of the above-mentioned <丨> to <3>, which is disposed on the light-receiving side of the photovoltaic cell. [Effects of the Invention] According to the present invention, it is possible to provide a photovoltaic cell encapsulating material which is maintained or improved in power generation when applied to a photovoltaic cell module, and which is advantageous in terms of the above-mentioned and other objects of the present invention. The features and advantages of the present invention can be further exemplified by the preferred embodiment, and the light-transmission m battery module includes at least a photovoltaic cell unit as a type of photovoltaic cell packaging material (wavelength). In the invention of the conversion type photovoltaic cell, the "wavelength conversion type first electric battery encapsulating material" is formed by laminating a first encapsulating layer containing no fluorescent substance and a ==: encapsulation layer. From the viewpoint of not containing the luminescent material encapsulation layer, the second-order q-forming of the side containing the wavelength-converted photoelectric maintenance of the two-layer structure of the j-to-two-cell description compared with the previous packaging material is The reason is not clear 'but the power generation efficiency is right to the photovoltaic module to emit light, then the % light material contained in the material absorbs light. This 4 r: side package, suction technology with (four) Material _4^#^^= This, even if the film thickness of the encapsulating material is made thicker, the material in which the phosphor material is present in the direction of the deeper material is actually less helpful in conversion.

f比較時，發電效率獲得如下結果:即便以π 表現出與膜厚較厚的情況同等或者其以上 I 進而，螢光物質的含量的減少會抑制 ;引 的光的減，使可見光穿透率增A。因此，崎 單元的光量增加，光電電池模組的光利用效 電= 高發電效率。 151可徒 本發明的波長轉換型光電電池封裝材料就崎效果的 201201384 觀點而言，第一封裝層以及第二封裝層的總厚度較佳為1〇 μιη〜1〇〇〇 μπι，更佳為 200 μηα〜800 μιη。 另外’就波長轉換效率的觀點而言，含有勞光物質的 第二封裝層的厚度較佳為1 μιη〜800 μιη，更佳為10 μιη 〜600 μιη。 逅吨，言頁蛍无物質的第二封裝層的厚度相對於第一 封裝層及第二封裝層的總厚度的比例較佳為G. 1%〜臟， 更佳為1%〜500/^ 含有螢光物質的第二封裝層中的螢光物質的濃度較理 想為根據螢光物質的麵等來適當調整。通常，於 Γ重量份，第二封裝層中的榮光物質的含有 量二1二_重量份〜30重量份，更佳為〇·_重 以I 份。藉由將上述含有率設為〇._重量份 玄波長轉換效率變得更充分，另外’藉由將上述入右 率設為10重詈伦ΤΑ . 稽由將上遗含有 光量的降低。 W進―一制到達光電電池單元的 進行邊參照圖式’―邊對本發明的光電電池模組 :3發明的光電電池模 圖1的光電電池模組中，於㈣帝丄㈣圖 側的表面具備保護玻璃料=幻〇的受光面 20並無特別 ’為了提高與下述所示的封裝:使用強化玻璃。 -著性，倾朗施物予質藉) 201201384 由壓印加工的凹凸式樣。保護玻璃20的受光側表面可為平 ;月，亦可為了提高太％光的導入效率，而施予凹凸形&amp;。 保護玻璃20與光電電池單元10之間具備封裝材料 3〇。圖1中的封裝材料30包含2層，光入射侧的第一封裝 層32為不含螢光物質的層，光電電池單元1〇側的第二封 裝層34為含有螢光物質的層。關於構成封裝材料3〇的材 料的詳細說明如下所述。 光電電池模組中，於光電電池單元1〇的背面側具備背 膜40。背膜40與光電電池單元10之間具備用於將&amp;電電 池單元保護封裝以免受到來自模組背面的衝擊等影響的背 面用封裝材料36。背面用封裝材料36只要是可將光電電 池單元保護封裝的材料，則並無特別限制，例如亦可應用 與不含螢光物質的第一封裝層32相同的材料。 圖1中雖未圖示，但進而於本發明的光電電池模組 中，亦可具有抗反射膜等通常設置於光電電池模組的構件。 〈波長轉換型光電電池封裝材料〉 以下’對本發明的波長轉換型光電電池封裝材料所使 用的物質進行詳細說明。 (螢光物質） 適用於本發明的螢光物質可列舉稀土類金屬的有機錯 合物。其中較佳為销錯合物或者釤錯合物，更佳為銷錯合 物。 藉由將銪錯合物用於螢光物質，可實現具有高發電效 率的光電電池模組。銪錯合物是將紫外線區域的光以高波When f is compared, the power generation efficiency is obtained as follows: even if π is expressed as the same as or thicker than the film thickness, the decrease in the content of the fluorescent substance is suppressed; the light loss is reduced, and the visible light transmittance is made. Increase A. Therefore, the amount of light in the unit is increased, and the light utilization efficiency of the photovoltaic cell module is high. The thickness of the first encapsulating layer and the second encapsulating layer is preferably 1 〇 μιη to 1 〇〇〇 μπι, more preferably, the wavelength conversion type photovoltaic cell encapsulating material of the present invention is from the viewpoint of 201201384. 200 μηα~800 μιη. Further, the thickness of the second encapsulating layer containing the working substance is preferably from 1 μm to 800 μm, more preferably from 10 μm to 600 μm, from the viewpoint of wavelength conversion efficiency. The ratio of the thickness of the second encapsulating layer having no substance to the total thickness of the first encapsulating layer and the second encapsulating layer is preferably G. 1% to dirty, more preferably 1% to 500/^. The concentration of the fluorescent substance in the second encapsulating layer containing the fluorescent substance is preferably adjusted as appropriate depending on the surface of the fluorescent substance or the like. Usually, the content of the glare substance in the second encapsulating layer is from 1-2 parts by weight to 30 parts by weight, more preferably 〇·_ in parts by weight. By setting the above-described content ratio to 〇. _ parts by weight, the conversion efficiency of the sinusoidal wavelength becomes more sufficient, and the above-mentioned rate of entering the right is set to 10 詈 詈 ΤΑ. In the photovoltaic cell module of the present invention, the photovoltaic cell module of the invention is in the photovoltaic cell module of FIG. 1 of the invention, and the surface of the image side of the (4) emperor (four) is shown in the figure. The light-receiving surface 20 having the protective frit = illusion is not particularly 'in order to improve the package shown below: tempered glass is used. - Sexuality, temptation to give material to borrow) 201201384 Embossed and embossed pattern. The light-receiving side surface of the cover glass 20 may be flat; or, in order to increase the introduction efficiency of too much light, the concavo-convex shape &amp; The sealing material 3 is provided between the protective glass 20 and the photovoltaic cell unit 10. The encapsulating material 30 in Fig. 1 comprises two layers, the first encapsulating layer 32 on the light incident side is a layer containing no fluorescent substance, and the second encapsulating layer 34 on the side of the photovoltaic cell unit 1 is a layer containing a fluorescent substance. A detailed description of the material constituting the encapsulating material 3 is as follows. In the photovoltaic cell module, a back film 40 is provided on the back side of the photovoltaic cell unit 1A. The back surface film 40 and the photovoltaic cell unit 10 are provided with a back surface sealing material 36 for protecting and packaging the &amp; battery cell from impact from the back surface of the module. The back surface sealing material 36 is not particularly limited as long as it can protect the photovoltaic cell unit from being packaged. For example, the same material as the first encapsulating layer 32 containing no fluorescent material can be applied. Although not shown in Fig. 1, in the photovoltaic module of the present invention, a member such as an antireflection film which is usually provided in a photovoltaic cell module may be provided. <Wavelength Conversion Photoelectric Cell Packaging Material> Hereinafter, the materials used in the wavelength conversion type photovoltaic cell encapsulating material of the present invention will be described in detail. (Fluorescent substance) The fluorescent substance to be used in the present invention is exemplified by an organic compound of a rare earth metal. Among them, a pin-compound or a ruthenium complex is preferable, and a pin-missing compound is more preferable. By using a ruthenium complex for a fluorescent substance, a photovoltaic cell module having high power generation efficiency can be realized. The 铕 complex is a high wave of light in the ultraviolet region

S 8 201201384 長轉換效率轉換為紅色的波長區域的光，該經轉換的光在 光電電池單元中有助於發電。 銪錯合物除了中心元素的銪（Eu)以外，需要成為配 位子的分子，本發明中配位子的種類並無限制，只要是與 銪形成錯合物的分子，則可為任一種分子。 包含如上所述的銪錯合物的螢光物質的一例可利用稀 土類錯合物，例如Eu(TTA)3phen等。Eu(TTA)3Phen的製 造方法例如可參照 Masaya Mitsuishi, Shinji Kikuchi，Tokuji Miyashita, Yutaka Amano, J.Mater.Chem. 2003, 13, 2875-2879中揭示的方法。 本發明中’並不限定錯合物的配位子，中性配位子較 佳為羧酸（carboxylic acid)、含氮有機化合物、含氮芳香 族雜環式化合物、β-二酮（p_diketone)類、或者氧化膦 (phosphine oxide ) ° 作為稀土類錯合物的配位子，可含有通式： R^COCHI^COR3 (式中’ R1表示芳基、烷基、環烷基、環 烧基烧基、芳烧基或者該些基團的取代體，R2表示氫原 子、烷基、環烷基、環烷基烷基、芳烷基或者芳基，妒表 示芳基、烧基、環烧基、環烧基烧基、芳烧基或者該些基 團的取代體）所表示的β-二酮類。 β-二酮類具體而言可列舉：乙醯基丙酮 (acetylacetone )、 全氟乙醯基丙酮 (perfluoroacetylacetone )、苯曱醯基-2-呋喃曱醯基曱烷 (benzoyl-2-furanoylmethane)、1，3-雙（3-吡啶基）-1，3-丙 9 201201384 二酮（l，3-bis(3-pyridyl)-l，3-propanedione)、笨曱醯基三氟 丙酮（benzoyl trifluoroacetone )、苯曱醯基丙 g同 (benzoylacetone)、5-氯續醯基-2-嘆吩甲醯基三氟丙酮 (5-chlorosulfonyl-2-thenoyl trifluoroacetone)、二（4-漠）苯 曱醯基曱烧（di(4-bromo)benzoylmethane)、二苯曱醯基甲 烧（dibenzoylmethane )、d，d-二樟腦基曱烧 (d，d-dicamphoryl methane )、1，3-二氰基-1,3-丙二酮 (l，3-dicyano-l，3-propanedione)、對雙（4, 4, 5, 5, 6, 6, 6-七 氟 -1,3- 己二 醯基） 苯 (p-bis(4,4,5,5,6,6,6-heptafluoro-l,3-hexanedioyl)benzene ) 、4,4’-二甲氧基二苯曱醯基甲烧（4,4’-dimethoxy dibenzoylmethane ) 、2, 6-二曱基-3,5-庚二酮 (2,6-dimethyl_3,5-heptanedione )、二萘曱酿基曱烧 (dinaphthoyl methane )、二特戊醯基曱烧（dipivaloyl methane )、雙（全氟-2-丙氧基丙醢基）曱烧 (bis(perfluoro-2-propoxypropionyl)methane )、1，3-二（2-0塞吩基）-1,3-丙二_( l，3-di(2-thienyl)-l，3_propandione)、 3-（三氟乙酿基）-d-樟腦（3-(trifluoroacetyl)-d-camphor)、 6,6,6-三氟-2,2-二曱基_3,5-己二嗣 ( 6,6,6-trifluoro-2,2-dimethyl-3,5-hexanedione ) 、 1,1,1, 2, 2, 6, 6, 7, 7, 7-十氟-3, 5-庚二酮 ( l，l，l，2,2,6,6,7,7,7-decafluoro-3,5-heptanedione ) 、 6, 6, 7, 7, 8, 8, 8_ 七氟 _2, 2_ 二曱基 _3, 5_ 辛二嗣 (6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione)、 201201384 2-σ夫°南基三歎丙酮（2-furyl trifluoroacetone )、六氣乙醯基 丙酮（hexafluoroacetyl acetone)、3-(七氟丁醢基）-d-樟腦 (3-(heptafluorobutyryl)-d-camphor)、4, 4, 5, 5, 6, 6, 6-七氟 -1_(2- D塞吩基 ）-1，3- 己二嗣 (4,4,5,5,6,6,6-heptafluoro-l-(2-thienyl)-l,3-hexanedione ) 、4-曱氧基二苯曱醯基甲烧（4-methoxy dibenzoyl methane )、4-曱氧基苯曱醯基-2- 0夫喃申醯基曱烧 (4-methoxybenzoyl-2-furanoyl methane)、6-甲基-2, 4-庚 二酮（6-methyl-2,4-heptanedione )、2-萘曱醯基三氟丙酮 (2-naphthoyl trifluoroacetone)、2-(2-°比〇定基）苯并口米嗤 (2-(2-pyridyl)benzimidazole )、5, 6-二經基-10-啡琳 (5,6-dihydroxy-10-phenanthroline)、1-苯基-3-曱基-4-苯 曱醢基 -5- 0比 嗤 (l-phenyl-3-methyl-4-benzoyl-5-pyrazole)、1-苯基-3-甲 基 -4-(4- 丁基苯甲醯基 ）-5- 吡唑 (l-phenyl-3-methyl-4-(4-butylbenzoyl)-5-pyrazole)、1-苯 基 -3- 甲基 -4- 異 丁醯基 -5- 吡唑 (l-phenyl-3-methyl-4-isobutyryl-5-pyrazole)、1-苯基-3-曱 基 -4- 三氟 乙酿基 _5_ °比 〇坐 (1-卩11611丫1-3-11161;11丫1-4七1£1\1〇1：〇&amp;。6171-5-烈以2〇16)、3-(5-苯 基-1,3,4-噁二唑-2-基）-2,4-戊二酮 (3-(5-phenyl-l,3,4-oxadiazol-2-yl)-2,4-pentanedione ) ' 3-苯基-2, 4-戊二酮（3-phenyl-2,4-pentanedione)、3-[3’，5’ -雙（苯基曱氧基）苯基]-1-(9-菲基）-1-丙烧-1,3-二酮 11 201201384 (3-[3',5'-bis(phenylmethoxy)phenyl]-1 -(9-phenanthryl)-1 -pr opane-l，3-dione )、5, 5-二曱基-1，1，1-三 lt-2, 4-己二酮 (5,5-dimethyl-l,l,l-trifluoro-2,4-hexanedione ) ' 1-苯基 -3-(2- 噻吩基 ）-1,3- 丙二酮 (l-phenyl-3-(2-t:hienyl)-l,3-propanedioiie)、3-(第三丁基 羥基亞 甲基 ）-d- 樟 腦 (3-(t-butylhydroxymethylene)-d-camphor ) ' 1, 1，1-三 |L -2,4-戊二酮（l，l，l_trifluoro-2,4-pentanedione )、 1，1，1，2, 2, 3, 3, 7，7, 8, 8, 9, 9，9-十四氟-4, 6-壬二嗣 (l，l，l，2,2,3,3,7,7,8,8,9,9,9_tetradecafluoro-4,6-nonanedione )、2,2,6,6-四 曱基-3,5-庚二酮 (2,2,6,6-tetramethyl-3,5-heptanedione )、4, 4, 4-三 It -1-(2- 萘 基 ）-1,3- 丁 二酉同 (4,4,4-trifluoro-l-(2-naphthyl)-1,3-butanedione ) ' 1,1,1-三氟 -5,5- 二曱基 -2,4- 己二酮 (l,l,l-trifluoro-5,5-dimethyl-2,4-hexanedione) ' 2, 2, 6, 6-四 曱 基 -3,5- 庚 二 酮 (2,2,6,6-tetramethyl-3,5-heptanedione)、2, 2, 6, 6-四曱基 -3, 5_辛二_ ( 2,2,6,6-tetramethyl-3,5-octanedione)、2, 2, 6-三曱基-3,5-庚二酮（2,2,6-trimethyl_3,5-heptanedione )、 2,2,7- 三 曱 基 _3,5- 辛二酮 (2,2,7-trimethyl-3,5-octanedione)、4, 4, 4-三氟-1-(°塞吩 基 ）-1，3- 丁二酮 (4,4,4-trifluoro-l-(thienyl)-1,3-butanedione 5 TTA) ' 1,3- 12 201201384, 二苯基-1，3-丙二酮（l，3-diphenyl-l，3-propanedione)、苯 甲醯基丙酮（benzoylacetone )、二苯曱醯基丙酉同 (dibenzoylacetone )、二異丁醯基曱烧（diisobutyryl methane )、二匕、六 口 &lt; 小曱烧（dipivaloyl methane )、3-曱 基戊烧-2, 4-二酮（3-methylpentane-2,4-dione)、2, 2-二曱 基戊烧-3, 5-二酮（2,2-dimethylpentane-3,5-dione)、2-曱基 -1，3- 丁二酮（2-methyl-l，3-butanedione )、1，3- 丁二 _ (1,3-butanedione ) 、 3-苯基-2,4-戊二酮 (3-phenyl-2,4-pentanedione )、1，1，1 -三氟-2, 4-戊二酮 (l，l,l-trifluoro_2,4-pentanedione)、1，1，1-三氣-5, 5-二曱 基 -2,4- 己二嗣 (l，l，l-trifluoro-5,5-dimethyl-2,4-liexanedione)、2, 2, 6, 6-四 甲 基 -3,5- 庚 二酮 (2,2,6,6-tetramethyl-3,5-heptanedione)、3-曱基-2, 4-戊二 酮（3-methyl-2,4-pentanedione)、2-乙醯基環戊酮（2-acetyl cyclopentanone ) ' 2-乙酿基環己 _ ( 2-acetyl cyclohexanone)、1-七氟丙基-3-第三丁基-1,3-丙二酮 (l-heptafluoropropyl-3-1&gt;butyl-l，3-propanedione)、1，3-二 本 基 -2- 曱 基 -1，3- 丙 二酉同 (l，3-diphenyl-2-metliyl-l，3-propanedione)、以及 1-乙氧基 -1,3-丁二_ (l-ethoxy-l，3-butanedione)等。 稀土類錯合物的中性配位子的含氮有機化合物、含氮 芳香族雜環式化合物、氧化膦，例如可列舉·· 1，10-啡啉 (l，10-phenanthroline)、(2-2’-bipyridyl)、 13 201201384 2-2’ -6, 2&quot;-三聯°比°定（2-2'-6,2”-terpyridyl) ' 4, 7-二苯基 -1，10-啡淋（4,7-diphenyl-l，10-phenanthroline)、2-(2-口比 咬基）苯并咪11 坐（2-(2-pyridyl)benzimidazole)、三笨基氧化 膦（triphenyl phosphine oxide )、三-正丁基氧化膦 (tri-n-butyl phosphine oxide )、三-正辛基氧化膦 (tri-n-octyl phosphine oxide )、磷酸三-正丁酯（tri_n_butyl phosphate)等。 上述螢光物質更佳為内包於樹脂粒子中（亦稱為球狀 螢光體）。構成上述樹脂粒子的單體化合物並無特別限制， 就光的散射抑制的觀點而言’較佳為乙烯基化合物。 另外，將上述螢光物質内包於樹脂粒子中的方法可無 特別限制地使用通常所使用的方法。例如，可藉由製備上 述螢光物質與構成樹脂粒子的單體化合物的混合物，將其 聚合而製備。具體而言，例如可藉由製備包含螢光物質及 乙烯基化合物的混合物，使用自由基聚合起始劑將乙烯基 化合物聚合，而構成作為内包有螢光物質的樹脂粒子（球 狀螢光體）的波長轉換用螢光材料。此外，本發明中所謂 波長轉換用螢光材料，是指將包含螢錢f的乙烯基化合 物聚合而獲得的狀態的材料。 就光利用效率提高的觀點而言，上述波長轉換用螢光 材料的平均粒徑較佳為〇. 001 μιη〜600 μιη，更佳為〇 〇〇5 μηι〜300 μιη，尤佳為 〇 〇1 μπι〜25〇 μηι。 ’、 · 波長轉換用螢光材料的平均粒徑可使用雷射繞射 粒度分布測絲置（·，Beekman c⑽如公司製造，S 8 201201384 Long conversion efficiency is converted to light in the red wavelength region, which contributes to power generation in photovoltaic cells. The ruthenium complex needs to be a molecule of a ligand in addition to the europium (Eu) of the central element. The type of the ligand in the present invention is not limited, and any one may be a molecule which forms a complex with ruthenium. molecule. As an example of the fluorescent substance containing the ruthenium complex as described above, a rare earth complex compound such as Eu(TTA)3phen or the like can be used. For the production method of Eu(TTA)3Phen, for example, the method disclosed in Masaya Mitsuishi, Shinji Kikuchi, Tokuji Miyashita, Yutaka Amano, J. Mater. Chem. 2003, 13, 2875-2879 can be referred to. In the present invention, the ligand of the complex is not limited, and the neutral ligand is preferably a carboxylic acid, a nitrogen-containing organic compound, a nitrogen-containing aromatic heterocyclic compound, or a β-diketone (p_diketone). ), or phosphine oxide ° as a ligand for rare earth complexes, may contain the general formula: R^COCHI^COR3 (wherein R1 represents an aryl group, an alkyl group, a cycloalkyl group, a ring-burning ring) a base group, an aryl group or a substituent of the groups, R2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an aralkyl group or an aryl group, and 妒 represents an aryl group, an alkyl group, or a ring. A β-diketone represented by a pyridyl group, a cycloalkyl group, an aryl group or a substituent of such groups. Specific examples of the β-diketones include: acetylacetone, perfluoroacetylacetone, benzoyl-2-furanoylmethane, 1,3-bis(3-pyridyl)-1,3-propane 9 201201384 diketone (l,3-bis(3-pyridyl)-l,3-propanedione), benzoyl trifluoroacetone ), benzoylacetone, 5-chlorosulfonyl-2-thenoyl trifluoroacetone, bis(4-indiyl) benzoquinone Di(4-bromo)benzoylmethane, dibenzoylmethane, d,d-d-dicamphoryl methane, 1,3-dicyano- 1,3-propanedione (l,3-dicyano-l,3-propanedione), p-bis(4, 4, 5, 5, 6, 6, 6-heptafluoro-1,3-hexanediyl) Benzene (p-bis(4,4,5,5,6,6,6-heptafluoro-l,3-hexanedioyl)benzene), 4,4'-dimethoxydiphenyl fluorenyl (4, 4'-dimethoxy dibenzoylmethane ), 2,6-dimercapto-3,5-heptanedione (2,6-dimethyl_3,5-heptanedione), dinaphthol Dinaphthoyl methane, dipivaloyl methane, bis(perfluoro-2-propoxypropionyl) methane, 1,3 -Bis (2-0-secenyl)-1,3-propanedi-(l,3-di(2-thienyl)-l,3_propandione), 3-(trifluoroethyl)-d-camphor (3 -(trifluoroacetyl)-d-camphor), 6,6,6-trifluoro-2,2-dimercapto-3,5-hexanedioxin (6,6,6-trifluoro-2,2-dimethyl-3 ,5-hexanedione ), 1,1,1, 2, 2, 6, 6, 7, 7, 7-decafluoro-3, 5-heptanedion (l,l,l,2,2,6,6 ,7,7,7-decafluoro-3,5-heptanedione ), 6, 6, 7, 7, 8, 8, 8_ sevoflurane_2, 2_dimercapto _3, 5_ xin bis (6,6, 7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione), 201201384 2-σ 夫 南 南 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- 2- Hexafluoroacetyl acetone), 3-(heptafluorobutyryl)-d-camphor, 4, 4, 5, 5, 6, 6, 6-heptafluoro-1_(2-D plug Phenyl)-1,3-hexamethylenediamine (4,4,5,5,6,6,6-heptafluoro-l-(2-thienyl)-l,3-hexanedione), 4-decyloxydiphenyl曱醯基甲烧4-methoxydibenzoyl methane), 4-methoxybenzoyl-2-furanoyl methane, 6-methyl-2,4-heptanedione (6) -methyl-2,4-heptanedione ), 2-naphthoyl trifluoroacetone, 2-(2-° 〇定定) 2-(2-pyridyl)benzimidazole , 5,6-dihydroxy-10-phenanthroline, 1-phenyl-3-indolyl-4-benzoin-5- 0 than hydrazine (l- Phenyl-3-methyl-4-benzoyl-5-pyrazole), 1-phenyl-3-methyl-4-(4-butylbenzylidene)-5-pyrazole (l-phenyl-3-methyl) 4-(4-butylbenzoyl)-5-pyrazole), 1-phenyl-3-methyl-4-isobutylidene-5-pyrazole (l-phenyl-3-methyl-4-isobutyryl-5-pyrazole) , 1-phenyl-3-indolyl-4-trifluoroethyl ketone _5_ ° than squat (1-卩11611丫1-3-11161; 11丫1-4 7 1£1\1〇1: 〇&amp;. 6171-5-Strong 2〇16), 3-(5-phenyl-1,3,4-oxadiazol-2-yl)-2,4-pentanedione (3-(5-phenyl-l) ,3,4-oxadiazol-2-yl)-2,4-pentanedione ) '3-phenyl-2,4-pentanedione, 3-[3',5 '-Bis(phenyldecyloxy)phenyl]-1-(9-phenanthryl)-1-propanol-1,3-dione 11 201201384 (3-[3',5'-bis(phenylmethoxy) Phenyl]-1 -(9-phenanthryl)-1 -pr opane-l,3-dione ),5,5-dimercapto-1,1,1-tri-lt-2,4-hexanedione (5, 5-dimethyl-l,l,l-trifluoro-2,4-hexanedione ) ' 1-phenyl-3-(2-thienyl)-1,3-propanedione (l-phenyl-3-(2- t:hienyl)-l,3-propanedioiie), 3-(t-butylhydroxymethylene)-d- camphor (3-(t-butylhydroxymethylene)-d-camphor ) ' 1, 1,1-three| L -2,4-pentanedione (l,l,l_trifluoro-2,4-pentanedione ), 1,1,1,2, 2, 3, 3, 7,7, 8, 8, 9, 9,9 -tetradecyl-4,6-anthracene (l,l,l,2,2,3,3,7,7,8,8,9,9,9_tetradecafluoro-4,6-nonanedione), 2, 2,6,6-tetradecyl-3,5-heptanedione (2,2,6,6-tetramethyl-3,5-heptanedione), 4, 4, 4-tri-I-(2-naphthalene) Base)-1,3-butadiene (4,4,4-trif Luoro-l-(2-naphthyl)-1,3-butanedione ) ' 1,1,1-trifluoro-5,5-dimercapto-2,4-hexanedione (l,l,l-trifluoro- 5,5-dimethyl-2,4-hexanedione) ' 2, 2, 6, 6-tetradecyl-3,5-heptanedione, 2,2,6,6-tetramethyl-3,5-heptanedione 2, 2, 6, 6-tetradecyl-3, 5_octyl 2 (2,2,6,6-tetramethyl-3,5-octanedione), 2, 2, 6-trimethyl-3,5 -2,2,6-trimethyl_3,5-heptanedione, 2,2,7-tridecyl-3,5-octanedione (2,2,7-trimethyl-3,5-octanedione) , 4, 4, 4-trifluoro-1-(°septyl)-1,3-butanedione (4,4,4-trifluoro-l-(thienyl)-1,3-butanedione 5 TTA) ' 1,3- 12 201201384, 1, 3-diphenyl-l, 3-propanedione, benzoylacetone, diphenyl hydrazino Dibenzoylacetone), diisobutyryl methane, diterpene, six-mouth &lt;dipivaloyl methane, 3-merpentanyl-2,4-dione (3-methylpentane-2,4- Dione), 2,2-dimethylpentane-3,5-dione, 2-mercapto-1,3-butanedione (2-methyl-) l,3-butanedi One ), 1,3-butanedione, 3-phenyl-2,4-pentanedione, 1,1,1-trifluoro -2, 4-pentanedione (l,l,tri-trifluoro_2,4-pentanedione), 1,1,1-tris-5- 5-diindolyl-2,4-hexanedione (l,l ,l-trifluoro-5,5-dimethyl-2,4-liexanedione), 2, 2, 6, 6-tetramethyl-3,5-heptanedione (2,2,6,6-tetramethyl-3, 5-heptanedione), 3-methyl-2,4-pentanedione, 2-acetylcyclopentanone '2-ethyl aryl ring 2-(2-acetylcyclohexanone), 1-heptafluoropropyl-3-tert-butyl-1,3-propanedione (l-heptafluoropropyl-3-1&gt;butyl-l, 3-propanedione), 1, 3-dibenzyl-2-mercapto-1,3-propanedione, and 1-ethoxy-1,3-butane _ (l-ethoxy-l, 3-butanedione) and the like. Examples of the nitrogen-containing organic compound, the nitrogen-containing aromatic heterocyclic compound, and the phosphine oxide of the neutral ligand of the rare earth complex are, for example, 1,10-phenanthroline, (2) -2'-bipyridyl), 13 201201384 2-2' -6, 2&quot;-triple ratio °(2-2'-6,2"-terpyridyl) ' 4, 7-diphenyl-1,10- 4,7-diphenyl-l,10-phenanthroline, 2-(2-pyridyl)benzimidazole, triphenyl phosphine Oxide), tri-n-butyl phosphine oxide, tri-n-octyl phosphine oxide, tri-n-butyl phosphate, etc. The fluorescent material is preferably contained in the resin particles (also referred to as a spherical phosphor). The monomer compound constituting the resin particles is not particularly limited, and is preferably a vinyl group from the viewpoint of light scattering suppression. Further, the method of encapsulating the above-mentioned fluorescent substance in the resin particles can be carried out by a method generally used without particular limitation. For example, the above-mentioned fluorescent dye can be prepared. A mixture of a monomer and a monomer compound constituting the resin particle is prepared by polymerizing it. Specifically, for example, a vinyl compound can be polymerized by using a radical polymerization initiator by preparing a mixture containing a fluorescent substance and a vinyl compound. In the present invention, a fluorescent material for wavelength conversion which is a resin particle (spherical phosphor) containing a fluorescent material is included. The fluorescent material for wavelength conversion in the present invention means a vinyl group containing a fluorescent powder f. The material of the state obtained by the polymerization of the compound. The average particle diameter of the above-mentioned wavelength conversion fluorescent material is preferably 0.001 μm to 600 μm, more preferably 〇〇〇5 μηι. 300 μιηη, especially preferably 〇〇1 μπι~25〇μηι. ', · The average particle size of the fluorescent material for wavelength conversion can be measured using a laser diffraction particle size distribution wire (·, Beekman c (10), manufactured by the company.

S 14 201201384 LS13320)來進行 本發明中所謂乙烯基化合物，只要是具有至 烯性不飽和賴化合物，則並無特舰制 = 地使用聚合反應時可形成乙歸基樹脂’尤其是忒 或者曱基丙烯酸樹脂的丙烯酸單體、曱基丙烯酸單體、= 烯酸寡聚物、曱基丙烯酸寡聚物等。本發明中較佳為可 舉丙烯酸單體、以及曱基丙烯酸單體等。 〜 ' 丙烯酸單體、以及曱基丙烯酸單體例如可列舉：丙 酸、曱基丙烯酸、該些酸的烷基酯，另外，亦可併用可與 該些單體共聚合的其他乙烯基化合物，可單獨使用丨種^、 亦可將2種以上組合使用。 丙稀酸烧基酯、以及甲基丙烯酸院基酯例如可列舉. 丙烯酸曱酯、曱基丙烯酸曱酯、丙烯酸乙酯、甲基丙歸酸 乙酯、丙烯酸丁酯、甲基丙烯酸丁酯、丙烯酸2-乙基己酸、 甲基丙烯酸2-乙基己酯等丙烯酸未經取代的烷基醋以及 甲基丙烯酸未經取代的烷基酯；（曱基）丙烯酸二環戊稀_ (dicyclopentenyl (meth)acrylate );(曱基）丙烯酸四氫糠酉旨 (tetrahydrofurfuryl (meth) acrylate );(曱基）丙稀酸节画旨 (benzyl (meth)acrylate);使α，β-不飽和叛酸在多元醇反應 而獲得的化合物（例如，聚乙二醇二（曱基）丙烯酸酉旨 (polyethylene glycol di(me1:h)acrylate)(伸乙基的數量為 2〜14的化合物）、三羥甲基丙烷二（曱基）丙烯醆略 (trimethylolpropane di(meth)acrylate )、三Μ 曱基丙燒三 (曱基）丙烯酸酯、三羥曱基丙烷乙氧基三（曱基）丙烯醆 15 201201384 酯、三經曱基丙烧丙氧基三（甲基）丙稀酸酯、四經甲基甲 烷三（甲基）丙烯酸酯、四羥甲基甲烷四（甲基）丙烯酸酯、 聚丙二醇二（曱基）丙烯酸酯（伸丙基的數量為2〜14的化 合物）、二季戍四醇五（甲基）丙稀酸酯（dipentaerythritol penta(meth)acrylate)、二季戊四醇六（曱基）丙烯酸酯、雙 酚A聚氧乙烯二（甲基）丙烯酸酯（bisphenol A polyoxyethylene di(meth)acrylate)、雙酴 A 二氧乙烯二（甲 基)丙烯酸酯、雙酚A三氧乙烯二（曱基)丙烯酸酯、雙酚a 十氧乙稀二（甲基)丙烯酸酯等）；使α，β-不飽和叛酸加成於 含縮水甘油基的化合物上而獲得的化合物（例如，三經甲 基丙烧三縮水甘油驗三丙稀酸酯（trimethylolpropane triglycidyl ether triacrylate)、雙酚 A 二縮水甘油醚二丙烯 酸酯等）；多元羧酸（例如，鄰苯二曱酸酐（phthalic anhydride))與具有羥基及乙烯性不飽和基的物質（例如， (曱基）丙婦酸β-羥基乙酯）的酯化物；胺基曱酸酯（曱基） 丙烯酸酯（urethane (meth)acrylate )(例如，曱苯二異氰酸 酯（tolylene diisocyanate)與（曱基）丙烯酸2-羥基乙酯的 反應物’二曱基六亞曱基二異氰酸g旨（trimethyl hexamethylene diisocyanate)、環己烷二曱醇（cycl〇hexane dimertianol)與（曱基）丙烯酸2-羥基乙酯的反應物等）；於 該些化合物的烧基上取代有羥基、環氧基、幽素基等的丙 烯酸經取代的烧基酯或者甲基丙烯酸經取代的烧基酯等。 另外，可與丙烯酸、甲基丙烯酸、丙烯酸烷基酯或者 甲基丙烯酸烷基酯共聚合的其他乙烯基化合物可列舉丙烯 201201384 醯胺（acrylamide )、丙稀腈（acryi〇nitriie)、二丙綱丙烯醯 胺（diacetone acrylamide)、苯乙烯（styrene)、乙烯基曱 苯（vinyl toluene)等。該些乙烯基單體可單獨使用j種， 亦可將2種以上組合使用。 本發明令的乙烯基化合物較佳為使用選自丙烯酸烷基 酯以及曱基丙烯酸烷基酯中的至少1種，更佳為使用選自 丙烯酸曱酯、曱基丙烯酸曱酯、丙烯酸乙酯、以及曱基丙 烯酸乙酯中的至少1種。 本發明中較佳為’為了使乙稀基化合物聚合而使用自 由基聚合起始劑。自由基聚合起始劑並無特別限制，可使 用通常所使用的自由基聚合起始劑。例如，較佳為列舉過 氧化物等。具體而言，較佳為藉由熱而產生游離自由基的 有機過氧化物。 有機化氧化物例如可使用：異丁基過氧化物（is〇butyl peroxide )、α，α’-雙（新癸醯基過氧化）二異丙基笨 (a，a’-bis(neodecanoylperoxy)diisopropylbenzene)、過氧化 新癸酸異丙苯S旨（cumyl peroxyneodecanoate )、過氧化二 石反酸二-正丙醋（bis-n-propyl peroxydicarbonate)、過氧化 二碳酸二-第二丁醋（bis-s-butyl peroxydicarbonate)、新癸 酸 1，1，3, 3-四曱基丁 g旨（l，l，3,3-tetramethylbutyl neodecanoate)、過氧化二碳酸雙（4-第三丁基環己基）酯 (bis(4-t-butyl cyclohexyl)peroxydicarbonate)、過氧化新癸 酸卜環己基-1-甲基乙酯（1-cylcohexyl-l-methyl ethyl peroxyneodecanoate )、過氧化二碳酸二_2-乙氧基乙醋 17 201201384 (bis-2-ethoxy ethyl peroxydicarbonate)、雙（乙基己基過氧 化）二碳酸酯（bis(ethyl hexyl peroxy)dicarbonate)、新癸酸 第三己酯（t-hexylneodecanoate)、過氧化二碳酸二曱氧基 丁醋（dimethoxy butyl peroxydicarbonate)、雙（3-曱基-3- 甲氧基丁基過氧化）二碳酸酉旨（bis(3-methyl-3-methoxy butyl peroxy)dicarbonate)、過氧化新癸酸第三丁酯、過氧 化特戊酸第三己酯（t-hexyl peroxypivalate )、3, 5, 5-三曱 基己酿基過氧化物（3,5,5-trimethyl hexanoyl peroxide)、辛 醯基過氧化物（octanoyl peroxide)、月桂醯基過氧化物 (lauroyl peroxide )、硬脂醯基過氧化物（stearoyl peroxide )、過氧化-2-乙基己酸1，1，3, 3-四曱基丁酯 (l，l，3,3-tetramethyl butyl peroxy-2-ethylhexanoate)、過氧 化琥珀酿（succinic peroxide)、2, 5-二甲基-2, 5-二（2-乙 基己醯基）己烷、過氧化-2-乙基己酸1-環己基-1-甲基乙 酯'過氧化-2-乙基己酸第三己酯、4-曱基苯甲醯基過氧化 物、過氧化-2-乙基己酸第三丁酯、間卜；μ才y彳小苯曱醯 基過氧化物、本曱酿基過氧化物、過氧化異丁酸第三丁酉旨、 1，1-雙（第三丁基過氧化）2-曱基環己烧、1，1_雙（第三己基 過氧化）-3, 3, 5-三曱基環己烷、1，1-雙（第三己基過氧化） 環己烷、1，1-雙（第三丁基過氧化）-3, 3, 5_三曱基環己烷、 1’ 1雙（第二丁基過氧化）環己銅、2，2_雙（4, 4_二丁基過氧 化環己基）丙烷、1，1-雙（第三丁基過氧化）環十二烷、過氧 化異丙基皁石反g夂第二己g旨（t_hexyl per〇XyiS〇pr〇pyl monocarbonate)、第三丁基過氧化順丁烯二酸、過氧化 18 201201384 -3, 5,5-三曱基己酸第 丁酯 t-butyl — j 曰曰 、 卜 per〇Xy-3,5,5-trimethyl hexanoate)、過氧化月桂酸第三丁 酯、2’ 5-二甲基-2, 5-雙（間甲苯甲酿基過氧化）己烧、過 化異丙基單碳酸第三丁酷、過氧化一2_乙基己基單碳酸第二 丁醋、過氧化苯曱酸第三己醋、2,5_二曱基 : 醯基過氧化）己燒、過氧化乙酸第三丁g旨、2,2省第(3 基過氧化）丁烷、過氧化苯甲酸第三丁酯、4 4-雙（第三 基過氧化）戊酸正丁酯、過氧化間苯二甲酸二_第三丁^ ⑽雙（第三丁基過氧化）二異丙基苯、二異^過^ 物、2, 5_二甲基-2, 5—雙（第三丁基過氧化）己烧第三丁義 異丙苯過氧化物、二-第三丁基過氧、對薄荷院氫過氧化ς (p-menthaiie hydroperoxide)、2, 5-二甲基_2, 5_雙（第三 基過氧化）己炔、二異丙基苯氫過氧化物、第三丁 ^烧基過氧化物、1，1，3, 3-四甲基丁基氫過氧化物、異^ 苯氫過氧化物、第三己基氫過氧化物、第三丁基氫過氧 物、2, 3-二曱基-2, 3-二苯基丁烷等。 自由基聚合起㈣的❹量可根據上述乙麟化 的種類或所形成的樹脂粒子的折射率等來適當選擇，^以 通常所使㈣使用量來使用具體而言，例如可相= 烯基化合物100重量份，則· i重量份〜15重量份使用， 較佳為以0. 5重量份〜1〇重量份使用。 本發明中的波長轉換用螢光材料是藉由將上述勞光物 質以及乙烯基化合物、視需要的過氧化物等自由美聚合起 始劑等加以混合，使螢光物質溶解或分散於乙烯二物 201201384 中，將其聚合而獲得。混合的方法並無特別限制，例如， 可藉由攪拌來進行。 螢光物質的較佳含量相對於乙烯基化合物1〇〇重量 份，較佳為0.001重量份〜30重量份，更佳為〇 〇1重量 份〜20重量份，尤佳為〇.〇丨重量份〜1〇重量份。 (分散介質樹脂） 本發明的波長轉換型光電電池封裝材料含有使上述螢 光物質或者上述波長轉換用螢光材料分散的分散介質樹 脂。分散介質樹脂的具體例子可列舉：丙烯酸系樹脂、聚 碳酸酯樹脂、聚苯乙烯樹脂、聚烯烴樹脂、聚氣乙烯樹脂、 聚醚砜（polyether sulfone)樹脂、聚芳 g旨（p〇iyarylate) 樹脂、聚乙烯基縮醛（polyvinyl acetal)系樹脂、環氧樹脂、 聚石夕氧樹脂、氟樹脂、該些樹脂的共聚物等。 上述分散介質樹脂可單獨使用1種，或者亦可將2種 以上組合使用。 上述丙烯酸系樹脂可列舉（甲基）丙烯酸酯樹脂等。聚 烯煙樹脂可列舉聚乙烯、聚丙烯等。聚乙烯基縮醛系樹脂 可列舉聚乙烯基曱酸·（polyvinyl f〇rmal)、聚乙烯基丁酸 (polyvinyl butyra卜 PVB 樹脂）、改質 PVB 等。 另外，所謂（甲基）丙烯酸酯樹脂，是指具有來自丙烯 酸醋或者甲基丙烯酸酯的結構單元的樹脂，丙烯酸烷基酯 或者曱基丙烯酸烧基酯例如可列舉：丙烯酸未經取代的烧 基醋或者曱基丙烯酸未經取代的烷基酯，或於該些化合物 的烷基上取代有羥基、環氧基、函素基等的丙烯酸經取代 201201384 的烧基s旨以及甲絲烯酸經取代攸基醋等。 丙烯酸醋或者曱基丙歸酸酿較佳為丙烯酸或者曱基丙 烯酸的碳數1〜10的烧基g旨，更佳為歧2〜8 基醋。 丙烯酸酉旨或者甲基丙稀酸醋具體而言可例示：甲基丙 烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸2_乙基己酯、甲 基丙稀酸2-祕乙i旨、曱基丙稀酸環己§旨、甲基丙稀酸笨 _、曱基丙烯酸节酯、丙烯酸甲g旨、丙稀酸乙醋、丙婦酸 丁醋、丙烯酸2-乙基己g旨、丙烯酸2_經基乙醋、丙稀酸環 己酉旨、丙稀酸本醋、丙稀酸节醋等。 (甲基)丙烯酸酯樹脂除了丙烯酸酯或者曱.基丙烯酸酯 以外’亦可使用可與該賴脂絲合的不絲單體而形成 共聚物。 上述不飽和單體可列舉：如曱基丙稀酸、丙稀酸之類 的不飽和酸類；苯乙烯、α—曱基苯乙烯、丙稀酿胺、二丙 酮丙烯_、丙騎、曱基丙烯腈、順丁烯二酸酐、笨基 順丁稀二麵胺、虹基順獨二邮料；亦可^ 而使用該些單體的2種以上。 該些不飽和單體可單獨使用！種，或者亦可將 上組合使用。 該些中，（曱基）丙稀酸賴脂較佳為具有來自丙稀酸 曱酉旨、丙稀酸乙醋、丙稀酸異丁醋、丙烯酸正丁g旨、 酸2-乙基己醋、曱基丙烯酸甲醋、以及甲基丙婦酸正丁㊉ 的結構單元的樹脂，就耐久性或通祕的觀點而言，更^ 為具有來自曱基丙烯酸曱酯的結構單元的樹脂。 21 201201384 共聚物㈣脂例如可列舉：（曱基）丙稀酸醋_苯 聚物、乙稀-乙酸乙稀酯共聚物（以下簡稱為eva)等^ 就财濕性或成本、通用性方面而言，分散介質樹 佳為EVA，另外，就耐久性及表面硬度的方面而言， 為（曱基）丙稀酸自旨樹脂。進而’ EVA與（甲基）丙婦酸 脂的併用就可兼具兩者的優點的觀點而言更佳。 曰' EVA較佳為乙酸乙烯酯單元的含有率為i重量百分比 (wt%)〜50 wt%，就螢光物質於封裝材料中的均勻分&amp;性 的方面而言’較佳為3 wt%〜35 wt%。 此外，就片材成形的觀點而言，較佳為EVA中的乙酸 乙烯Sa單元的含有率為10 wt%〜50 wt%，更佳為20 wt% 〜35 wt%。 EVA可應用市售品’市售品例如可列舉：T〇s〇h (股）S 14 201201384 LS13320) The vinyl compound in the present invention is used as long as it has a olefinic unsaturated lysate compound, and there is no special ship system. When a polymerization reaction is used, an ethyl group-based resin can be formed, especially ruthenium or osmium. Acrylic acid-based acrylic monomer, mercaptoacrylic acid monomer, = enoic acid oligomer, methacrylic acid oligomer, and the like. In the present invention, an acrylic monomer, a mercaptoacrylic monomer or the like is preferably used. Examples of the 'acrylic monomer and the mercaptoacrylic acid monomer include propionic acid, mercaptoacrylic acid, alkyl esters of these acids, and other vinyl compounds copolymerizable with the monomers may be used in combination. The above species may be used alone or in combination of two or more. Examples of the acrylic acid ester and the methacrylic acid ester ester include decyl acrylate, decyl methacrylate, ethyl acrylate, ethyl propyl acrylate, butyl acrylate, and butyl methacrylate. Acrylic acid unsubstituted alkyl vinegar such as 2-ethylhexanoic acid acrylate or 2-ethylhexyl methacrylate and unsubstituted alkyl methacrylate; dicyclopentenyl (mercapto) acrylate (meth)acrylate ); (曱) tetrahydrofurfuryl (meth) acrylate; (benzyl) benzyl (meth)acrylate; makes α,β-unsaturated rebellion a compound obtained by reacting an acid with a polyhydric alcohol (for example, polyethylene glycol di(me1:h)acrylate) (a compound having an ethyl group of 2 to 14), and three Trimethylolpropane di(meth)acrylate, trimethyl sulfonium tris(decyl) acrylate, trishydroxypropyl propane ethoxy tris(decyl) propylene oxime 15 201201384 Ester, tri-propyl propyl propyl propyl tri(methyl) acrylate, Tetramethylmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, polypropylene glycol bis(indenyl)acrylate (compounds with a number of propyl groups of 2 to 14), second season Dipentaerythritol penta (meth)acrylate, dipentaerythritol hexa(meth) acrylate, bisphenol A polyoxyethylene di (bisphenol A polyoxyethylene di (bisphenol A polyoxyethylene di) Meth)acrylate), biguanide A dioxyethylene di(meth)acrylate, bisphenol A trioxyethylene bis(indenyl) acrylate, bisphenol a decaethoxyethylene di(meth)acrylate, etc.; A compound obtained by adding α,β-unsaturated tickic acid to a glycidyl group-containing compound (for example, trimethylolpropane triglycidyl ether triacrylate, bisphenol) A diglycidyl ether diacrylate, etc.; a polycarboxylic acid (for example, phthalic anhydride) and a substance having a hydroxyl group and an ethylenically unsaturated group (for example, (mercapto)-proacetoic acid β-) Esterification of hydroxyethyl ester ; urethane (meth)acrylate (for example, the reaction of tolylene diisocyanate with 2-hydroxyethyl (meth)acrylic acid' dimercaptohexa a reaction of trimethyl hexamethylene diisocyanate, cyclohexane dimertianol and 2-hydroxyethyl (meth)acrylic acid; An acrylic acid-substituted alkyl ester or a methacrylic acid-substituted alkyl ester having a hydroxyl group, an epoxy group, a leuco group or the like is substituted. Further, other vinyl compounds which can be copolymerized with acrylic acid, methacrylic acid, alkyl acrylate or alkyl methacrylate include propylene 201201384 acrylamide, acrylonitrile (acryi〇nitriie), diacetyl. Diacetone acrylamide, styrene, vinyl toluene, and the like. These vinyl monomers may be used alone or in combination of two or more. The vinyl compound of the present invention is preferably at least one selected from the group consisting of alkyl acrylates and alkyl methacrylates, and more preferably selected from the group consisting of decyl acrylate, decyl methacrylate, ethyl acrylate, And at least one of ethyl methacrylate. In the present invention, it is preferred to use a free radical polymerization initiator for the polymerization of the ethylenic compound. The radical polymerization initiator is not particularly limited, and a radical polymerization initiator which is usually used can be used. For example, a peroxide or the like is preferably exemplified. Specifically, an organic peroxide which generates free radicals by heat is preferred. For the organic oxide, for example, isbutyl peroxide, α,α'-bis(nesulfonyl peroxy)diisopropylcanyl (a, a'-bis (neodecanoylperoxy) can be used. Diisopropylbenzene), cumyl peroxyneodecanoate, bis-n-propyl peroxydicarbonate, di-peracetic acid dihydrate -s-butyl peroxydicarbonate), 1,1,3,3-tetramethylbutyl neodecanoate, bis(4-tert-butylcyclohexane peroxide) Bis(4-t-butyl cyclohexyl)peroxydicarbonate, 1-cylcohexyl-l-methyl ethyl peroxyneodecanoate, di-2-carboperate -ethoxy ethoxyacetate 17 201201384 (bis-2-ethoxy ethyl peroxydicarbonate), bis(ethyl hexyl peroxy)dicarbonate, t-hexylneodecanoate ), dimethoxy butyl peroxydicarbonate, double Bis(3-methyl-3-methoxy butyl peroxy)dicarbonate, perbutyl neodecanoate dibutyl acrylate, peroxidic pivalic acid T-hexyl peroxypivalate, 3,5,5-trimethyl hexanoyl peroxide, octanoyl peroxide, laurel Lauroyl peroxide, stearoyl peroxide, 1,1,3, 3-tetradecyl butyl peroxy-2-ethylhexanoate (l, l, 3, 3) -tetramethyl butyl peroxy-2-ethylhexanoate), succinic peroxide, 2, 5-dimethyl-2, 5-di(2-ethylhexyl)hexane, peroxy-2-ethyl 1-cyclohexyl-1-methylethyl hexanoate-tert-hexyl peroxy-2-ethylhexanoate, 4-mercaptobenzylidene peroxide, peroxy-2-ethylhexanoic acid Third butyl ester, inter-bu; μ y 彳 彳 曱醯 曱醯 过氧化物 过氧化物 、 、 、 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 曱 1, 1, 1, 1, 1, 1, 1, 1, 1, Oxidation) 2-mercaptocyclohexene, 1,1_bis (third hexyl peroxygen) -3,3,5-trimethylcyclohexane, 1,1-bis(trihexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3, 5_trimethylcyclohexane, 1' 1 double (second butyl peroxy) cyclohexyl copper, 2,2-bis(4,4-dibutylperoxycyclohexyl)propane, 1,1-double (T-butyl peroxy) cyclododecane, isopropyl saponin, anti-g 夂 己 夂 ( (t_hexyl per〇XyiS〇pr〇pyl monocarbonate), tert-butyl peroxybutylene Acid, peroxidation 18 201201384 -3, 5,5-tridecylhexanoate t-butyl — j 曰曰, 〇per〇Xy-3,5,5-trimethyl hexanoate), oxidized lauric acid third Butyl ester, 2' 5-dimethyl-2, 5-bis(m-toluene), calcined, isopropylated monocarbonate, tributyl, peroxy-2-ethylhexyl monocarbonate Second vinegar, benzoic acid, third vinegar, 2,5-didecyl: sulfhydryl peroxide, hexane, peroxyacetic acid, third butyl, 2, 2 (3) peroxidation Butane, tert-butyl peroxybenzoate, 4 4-bis(third-based peroxy)-n-butyl valerate, isophthalic acid peroxide Formic acid di-tertiary (10) bis(t-butylperoxy)diisopropylbenzene, diiso- benzene, 2,5-dimethyl-2,5-bis (t-butyl peroxidation) ) burnt third butyl cumene peroxide, di-t-butylperoxy, p-menthaiie hydroperoxide, 2, 5-dimethyl-2, 5_ double (third base peroxidation) hexyne, diisopropylbenzene hydroperoxide, third butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, iso^ Benzene hydroperoxide, third hexyl hydroperoxide, tert-butyl hydroperoxide, 2,3-dimercapto-2, 3-diphenylbutane, and the like. The amount of the radicals in the radical polymerization (4) can be appropriately selected depending on the type of the above-mentioned acetylene or the refractive index of the resin particles to be formed, etc., and is usually used in the amount of (iv) used, specifically, for example, a phase = alkenyl group The compound is used in an amount of 0.5 parts by weight to 1 part by weight, preferably 0.5 parts by weight to 1 part by weight. The fluorescent material for wavelength conversion in the present invention is obtained by mixing the above-mentioned light-emitting substance, a vinyl compound, an optional peroxide-based polymerization initiator or the like, and dissolving or dispersing the fluorescent substance in ethylene. In 201201384, it was obtained by polymerization. The method of mixing is not particularly limited and, for example, it can be carried out by stirring. The content of the fluorescent substance is preferably from 0.001 part by weight to 30 parts by weight, more preferably from 1 part by weight to 20 parts by weight, based on 1 part by weight of the vinyl compound, more preferably 〇. Parts ~ 1 part by weight. (Dispersion Medium Resin) The wavelength conversion type photovoltaic cell encapsulating material of the present invention contains a dispersion medium resin which disperses the above-mentioned fluorescent substance or the above-mentioned wavelength conversion fluorescent material. Specific examples of the dispersion medium resin include an acrylic resin, a polycarbonate resin, a polystyrene resin, a polyolefin resin, a polystyrene resin, a polyether sulfone resin, and a polyfluorene resin. Resin, polyvinyl acetal resin, epoxy resin, polyoxin, fluororesin, copolymer of these resins, and the like. The above-mentioned dispersion medium resins may be used singly or in combination of two or more kinds. The acrylic resin may, for example, be a (meth) acrylate resin. Examples of the polyolefin resin include polyethylene, polypropylene, and the like. Examples of the polyvinyl acetal resin include polyvinyl f〇rmal, polyvinyl butyra (PVB resin), and modified PVB. Further, the (meth) acrylate resin refers to a resin having a structural unit derived from acryl vinegar or methacrylate, and an alkyl acrylate or a mercapto acrylate is exemplified by an unsubstituted alkyl group of acrylic acid. An unsubstituted alkyl ester of vinegar or methacrylic acid, or an acrylic acid substituted with a hydroxyl group, an epoxy group, a functional group or the like on the alkyl group of the compounds, substituted by the alkyl group of 201201384 and the methylated acid Replace thiol vinegar and so on. The acrylic vinegar or the mercaptopropionic acid is preferably a ketone of 1 to 10 carbon atoms of acrylic acid or mercaptoacrylic acid, more preferably 2 to 8 vinegar. Specific examples of the acrylic acid or methyl acrylate vinegar include ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and methyl acrylate.曱 丙 丙 丙 、 、 、 、 、 、 、 、 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基 甲基Acrylic acid 2_ by base ethyl vinegar, acrylic acid cyclohexanide, acrylic acid vinegar, acrylic acid vinegar and the like. The (meth) acrylate resin may be a copolymer other than the acrylate or the oxime acrylate. The above unsaturated monomer may, for example, be an unsaturated acid such as mercaptoacrylic acid or acrylic acid; styrene, α-mercaptostyrene, acrylamide, diacetone propylene, propylene, sulfhydryl Acrylonitrile, maleic anhydride, stupid butadiene dihedylamine, and Hongji Shun Duo Mail; or two or more of these monomers may be used. These unsaturated monomers can be used alone! Kind, or can be used in combination. Among these, (mercapto) lysine lysate preferably has the meaning of acrylate, acetoacetate, acetoacetic acid, butyl acrylate, acid 2-ethylhexyl The resin of the structural unit of vinegar, methacrylic acid methyl vinegar, and methyl propyl acetoacetate is more preferably a resin having a structural unit derived from decyl methacrylate from the viewpoint of durability or transparency. 21 201201384 The copolymer (iv) ester may, for example, be a (mercapto) acrylic acid vinegar _ benzene polymer, a ethylene-ethylene acetate copolymer (hereinafter referred to as eva), etc. in terms of richness or cost, and versatility. In particular, the dispersion medium tree is preferably EVA, and is a (mercapto)acrylic acid-based resin in terms of durability and surface hardness. Further, it is more preferable that the combination of EVA and (meth) propyl acrylate can have both advantages.曰' EVA is preferably a vinyl acetate unit content of i weight percent (wt%) to 50 wt%, preferably 3 wt% in terms of uniformity and affinity of the phosphor material in the encapsulating material. %~35 wt%. Further, from the viewpoint of sheet forming, the content of the vinyl acetate Sa unit in the EVA is preferably from 10 wt% to 50 wt%, more preferably from 20 wt% to 35 wt%. EVA can be applied to commercial products. 'Commercial products can be cited, for example, T〇s〇h (shares)

製造的 Ultrathene、Mitsui Dupont Polychemical 股份有限公 司製造的Evaflex、Asahi Kasei Chemicals公司製造的 Suntec EVA、Ube-Maruzen Polyethylene 公司製造的 UBE EVA共聚物、住友化學（Sumitomo Chemical)公司製造的 Evertate、Japan Polyethylene 公司製造的 Novatec EVA 等。 於將EVA與甲基丙烯酸甲酯併用的情況，相對於EVA 與甲基丙烯酸甲酯的總量1〇〇重量份，EVA的含有率較佳 為50重量份以上，更佳為70重量份以上。 進而’上述分散介質樹脂亦可添加交聯性單體而製成 具有交聯結構的樹脂。 交聯性單體例如可列舉：使α,β-不飽和羧酸在多元醇Manufactured by Ultrathene, Evaflex manufactured by Mitsui Dupont Polychemical Co., Ltd., Suntec EVA manufactured by Asahi Kasei Chemicals Co., Ltd., UBE EVA copolymer manufactured by Ube-Maruzen Polyethylene Co., Ltd., and Everate manufactured by Sumitomo Chemical Co., Ltd., manufactured by Japan Polyethylene Co., Ltd. Novatec EVA et al. When EVA is used in combination with methyl methacrylate, the content of EVA is preferably 50 parts by weight or more, and more preferably 70 parts by weight or more based on 1 part by weight of the total amount of EVA and methyl methacrylate. . Further, the dispersion medium resin may be added with a crosslinkable monomer to form a resin having a crosslinked structure. The crosslinkable monomer is exemplified by making an α,β-unsaturated carboxylic acid in a polyol.

S 22 201201384 反應而獲得的化合物（例如，聚乙二醇二（曱基）丙稀酸酯 (伸乙基的數量為2〜14的化合物）、三經曱基丙烧二（曱 基）丙烯酸酯、三羥曱基丙烷三（甲基）丙烯酸酯、三羥曱基 丙烷乙氧基三（甲基）丙烯酸酯、三羥曱基丙烷丙氧基三（曱 基）丙烯酸酯、四羥甲基甲烷三（曱基）丙烯酸酯、四羥曱基 甲烷四（甲基）丙烯酸酯、聚丙二醇二（曱基）丙烯酸酯（伸 丙基的數量為2〜14的化合物）、二季戊四醇五（甲基）丙烯 酸酯、二季戊四醇六（甲基）丙稀酸酯、雙酷A聚氧乙稀二 (甲基）丙烯酸酯、雙酚A二氧乙烯二（甲基）丙烯酸酯、雙 紛A二氧乙浠一（曱基）丙烯酸g旨、雙盼a十氧乙稀二（曱 基）丙烯酸目旨等）；使α，β-不飽和羧酸加成於含縮水甘油基 的化合物上而獲得的化合物（例如，三輕曱基丙烧三縮水 甘油醚二丙烯酸酯、雙紛Α二縮水甘油醚二丙烯酸酯等）； 多元羧酸（例如’鄰苯二曱酸酐）與具有羥基及乙烯性不 飽和基的物質（例如’（曱基）丙烯酸|3_羥基乙酯）的酯化 物；胺基曱酸酯（甲基）丙烯酸酯（例如，甲笨二異氰酸酯 與（甲基）丙烯酸2-羥基乙酯的反應物，三曱基六亞甲基二 異氰酸酯、環己烷二甲醇與（曱基）丙烯酸2-羥基乙酯的反 應物等）等。 特佳的交聯性單體可列舉：三羥曱基丙烷三（曱基）丙 烯酸酯、二季戊四醇四（曱基）丙烯酸酯、二季戊四醇六（曱 基）丙烯酸酯、雙酚A聚氧乙烯二曱基丙烯酸酯。 此外’上述交聯性單體可單獨使用1種，或者將2種 以上組合使用。 23 201201384 人缸Πί質樹脂可藉由在上述單體中添加自由基聚 :β 、仃加熱或者光照射而聚合，或者具有交聯結 構。 .上述自由基聚合起始劑並無特別限制，可使用通常所 使用的自由基聚合起始劑。例如可列舉上述過氧化物等。 就流動性的觀誠言，上述分散介質樹㈣重量平均 分子量較佳為1〇，刚〜議，咖，更佳為1〇，_〜5〇，麵。 本發明的波長轉換型光電電池封裝材料中，除上述以 外’亦可視需要而含有紫外線吸收劑、偶合劑、塑化劑、 阻燃劑、抗氧化劑、光穩㈣、防錄劑、加JL助劑等。 本發明的波長轉換型光電電池封裝材料可利用公知的 技術來製造。例如可利用：將至少熔融混練有上述螢光物 質或者波長轉換用螢光材料（球狀螢光體）以及分散介質 樹脂、進而視需要的其他添加劑的組成物成型為片材狀的 方法；或者將上述分散介質樹脂製成清漆並添加上述螢光 物質或者波長轉換用螢光材料（球狀螢光體）後，成型為 片材狀，然後去除溶劑的方法等。 具體而言，例如，經由間隔片使2片脫模片材對向， 向形成於2片脫模片材間的空隙中添加上述熔融混練之組 成物，自兩侧進行熱壓製而形成第二封裝層，進而利用同 樣的方法形成其中不含螢光物質的第一封裝層，將該第二 封裝層與第一封裝層積層，然後將其失持於脫模片材中， 自兩側進行熱壓製，藉此獲得波長轉換型光電電池封裝材 料。S 22 201201384 The compound obtained by the reaction (for example, polyethylene glycol bis(indenyl) acrylate (a compound having an ethyl group of 2 to 14), and tris-propyl propyl bis(indenyl) acrylate Ester, trishydroxypropyl propane tri(meth) acrylate, trishydroxypropyl propane ethoxy tri(meth) acrylate, trishydroxypropyl propane propoxy tri(decyl) acrylate, tetrahydroxyl Methane tris(fluorenyl) acrylate, tetrahydroxymethane methane tetra(meth) acrylate, polypropylene glycol bis(indenyl) acrylate (a compound having a propyl group of 2 to 14), dipentaerythritol 5 ( Methyl) acrylate, dipentaerythritol hexa(methyl) acrylate, bis-A polyoxyethylene di(meth) acrylate, bisphenol A dioxyethylene di(meth) acrylate, double s Dioxetane-(indenyl)acrylic acid, double-anti-a-oxyethylene bis(indenyl)acrylic acid, etc.; addition of α,β-unsaturated carboxylic acid to glycidyl-containing compounds And the obtained compound (for example, trisaloxime-propyl triglycidyl ether diacrylate, double Diglycidyl ether diacrylate, etc.; an ester of a polycarboxylic acid (such as 'phthalic anhydride) and a substance having a hydroxyl group and an ethylenically unsaturated group (for example, '(mercapto)acrylic acid|3_hydroxyethyl ester) Amino phthalate (meth) acrylate (for example, a reaction of methyl diisocyanate with 2-hydroxyethyl (meth) acrylate, trimethyl hexamethylene diisocyanate, cyclohexane dimethanol A reaction product with (nonyl) 2-hydroxyethyl acrylate, etc.). Particularly preferred crosslinkable monomers are: trishydroxypropyl propane tris(fluorenyl) acrylate, dipentaerythritol tetrakis(meth) acrylate, dipentaerythritol hexakisyl acrylate, bisphenol A polyoxyethylene Dimercapto acrylate. Further, the above-mentioned crosslinkable monomers may be used singly or in combination of two or more kinds. 23 201201384 A human cylinder Π a resin can be polymerized by adding a radical poly: β, hydrazine heating or light irradiation to the above monomer, or has a crosslinked structure. The above-mentioned radical polymerization initiator is not particularly limited, and a radical polymerization initiator which is usually used can be used. For example, the above-mentioned peroxide etc. are mentioned. As far as the liquidity is concerned, the above-mentioned dispersion medium tree (4) preferably has a weight average molecular weight of 1 〇, just about, and coffee, more preferably 1 〇, _~5 〇, face. The wavelength conversion type photovoltaic cell encapsulating material of the present invention may contain, in addition to the above, an ultraviolet absorber, a coupling agent, a plasticizer, a flame retardant, an antioxidant, a light stabilizer (four), an anti-recording agent, and a JL assist. Agents, etc. The wavelength conversion type photovoltaic cell encapsulating material of the present invention can be produced by a known technique. For example, a method of molding a composition in which at least the above-described fluorescent substance or wavelength conversion fluorescent material (spherical phosphor), a dispersion medium resin, and optionally other additives are melt-kneaded into a sheet shape can be used; or The dispersion medium resin is made into a varnish, and the above-mentioned fluorescent substance or wavelength conversion fluorescent material (spherical phosphor) is added, and then formed into a sheet shape, and then the solvent is removed. Specifically, for example, two release sheets are opposed via a spacer, and the melt-kneaded composition is added to a space formed between the two release sheets, and hot pressed from both sides to form a second Encapsulating the layer, and then forming a first encapsulation layer containing no fluorescent substance by the same method, laminating the second encapsulation layer and the first encapsulation layer, and then holding it in the release sheet, from both sides Hot pressing, thereby obtaining a wavelength conversion type photovoltaic cell encapsulating material.

S 24 201201384 〈光電電池模組〉 ▲本發明中，光電電池模組是由抗反射膜（未圖示）、保 護玻璃2G、上述所說明的波長轉換型光電電池封裝材料 30、光電電池單元10、背面用封裝材料36、背膜、單 元電極（未圖示）、標記線（未圖示）等必要構件所構成。 該些構件中，較光電電池單元1〇更存在於光入射側的 構件為抗反射膜（未圖示）、保護玻璃2()、本發明的波長 轉換型光電電池封裝材料30，是以此順序設置。 本發明的光電電池模組中，為了使自所有角度進入的 外部光的反射損失少’且效率良好地導入至光電電池單元 ，，波長轉換型光電電池封裝材料3G的折射率較佳為高於 較該波長轉翻光f電池縣材料3G更配置於光入射側 的透光性層’即抗反射膜、保護玻璃2〇等的折射率，且低 於較該波長轉換型光電電池雜材料3{)更配置於反光入 射側的透光性層，即單元反射防賴（未圖示）以及包含 Si等的光電電池單元1〇的折射率。 ▲ “即，本發明的光電電池模組中，光電電池單元丨〇以及 ^光電電池單it 10更設置於光人射側的層（例如，保護玻 =20、較保護玻璃2G更設置於光人射_抗反射膜（未 =)等）t ’設置於接近光f電池單元1()之侧的層的折 為相其而設置於先入射側的層的折射率 «•羊、’、田而。’較理想為，當光電電池單元1〇卩及較 %池單元10更設置於光人射側的層包含m層（m為2以 25 201201384 上）’將上述m個層的各自崎射率自光人射側依序設為 二、广、.，·…、U、、時……$κη〇ι成立。 此外，本發明的波長轉換型光電電池封裝材料3〇為以2 層以上的封裝㈣成，故而較理想為2層封 亦滿足上述_。 具體而言，較波長轉換型光電電池封裝材料3Q更配置 於光入射側的透光性層，即抗反射膜的折射率使用125〜 1. 45，保護玻璃20的折射率通常使用丨45〜1. 55左右。 配置於該波長轉㈣光電電池封裝材_反光人射侧的透 光性層，枚電電池單元料认射防賴晴射率通常 使用1. 9〜2. 1左右，以及構成光電電池單元的&amp;層 折射率通常使用3. 3〜3.4左右。 此外，透光性層的其他層的較佳折射率如以下所示。 例如較佳為’當自透光性層的光入射側起將3層設為a層、 b層、c層時’各層的折射率na、nb、nc^足或者近似於 下述式（1)。 、 nb= (na.nc) 05 此外，日本專利申請2010-120647的揭示是藉由來昭 而將其整體併入本說明書中。 …、、 η本說明書中記載的所有文獻、糊申請、以及技術規 格是與具體且分敢載將各文獻、專财請、以及技術規 格藉由參照*併人的纽相@减地，藉由參照而併入本S 24 201201384 <Photovoltaic Cell Module> In the present invention, the photovoltaic cell module is composed of an antireflection film (not shown), a cover glass 2G, the above-described wavelength conversion type photovoltaic cell encapsulating material 30, and photovoltaic cell unit 10. It is composed of a necessary member such as a back surface sealing material 36, a back film, a unit electrode (not shown), and a marking line (not shown). Among these members, the member which is present on the light incident side more than the photovoltaic cell unit 1 is an antireflection film (not shown), the cover glass 2 (), and the wavelength conversion type photovoltaic cell encapsulant 30 of the present invention. Order settings. In the photovoltaic cell module of the present invention, in order to reduce the reflection loss of external light entering from all angles and efficiently introduce it into the photovoltaic cell, the refractive index of the wavelength conversion type photovoltaic cell encapsulating material 3G is preferably higher than The refractive index of the light transmissive layer disposed on the light incident side, that is, the antireflection film, the protective glass 2 , etc., is lower than that of the wavelength conversion type photovoltaic cell 3 {) The translucent layer disposed on the light-reflecting incident side, that is, the refractive index of the unit reflection preventing (not shown) and the photovoltaic cell unit 1 including Si or the like. ▲ "In the photovoltaic module of the present invention, the photovoltaic cell unit 丨〇 and the photovoltaic cell single it 10 are further disposed on the light-emitting side layer (for example, the protective glass = 20, and the protective glass 2G is disposed on the light) The refractive index «•羊, ', which is disposed on the side of the first incident side of the layer which is disposed on the side close to the light cell 1 (), and the layer of the anti-reflection film (not =) Preferably, when the photovoltaic cell unit 1 and the cell unit 10 are disposed on the light-emitting side, the layer includes m layers (m is 2 to 25 201201384) 'the respective m layers The saturation rate is set to two, wide, ., ..., U, and ... $κη〇ι in order from the light-emitting side. Further, the wavelength conversion type photovoltaic cell encapsulating material of the present invention is 3 The above-mentioned package (4) is formed, and therefore it is preferable that the two-layered package also satisfies the above-mentioned _. Specifically, the light-transmissive layer disposed on the light incident side, that is, the refraction of the anti-reflection film, is more disposed than the wavelength-converting photovoltaic cell packaging material 3Q. The rate of use of 125 to 1. 45, the refractive index of the protective glass 20 is usually used 丨 45~1. 55 or so. Photovoltaic cell encapsulation material _ reflective light-emitting layer on the side of the human body, the illuminating cell unit material is usually used at a rate of 1. 9~2. 1 and the refractive index of the layer forming the photovoltaic cell is usually Further, the preferred refractive index of the other layers of the light-transmitting layer is as follows. For example, it is preferable to set the three layers to the a layer from the light incident side of the light-transmitting layer. In the case of the b layer and the c layer, the refractive indices na, nb, and nc of each layer are sufficient or approximate to the following formula (1). nb = (na.nc) 05 In addition, the disclosure of Japanese Patent Application No. 2010-120647 is The entire disclosure of this document is incorporated herein by reference. Referring to *the person's new phase @减地, incorporated by reference

S 26 201201384 說明書中。 [實例] ，但本發 以下’利用實例對本發明進行更詳細的說明 明並不限定於該些實例。 [實例1 ] 〈螢光物質的合成〉 將200 mg &amp; 4,4,4-三敦+(。塞吩基H，3_丁二胸 (ΠΑ)溶解於7ml的乙醇中，向其中添加1撾的氫氡化 鈉M ml加以混合。將溶解於7 ml乙醇中的6.2 ^^的 1，10-啡啉添加於之前的混合溶液中，攪拌1小時後，添加 含有10311^的£11(：13.6112〇的3.51111水溶液，獲得沈澱物。 將該沈澱物過遽分離’以乙醇清洗’並乾燥，從而獲得蟹 光物質 Eu(TTA)3Phen。 〈波長轉換用螢光材料（球狀螢光體）的製備〉 使用0.3重量份作為螢光物質的上述所得的 Eu(TTA)3Phen、60重量份作為乙烯基化合物的甲基丙稀酸 甲酯、0.012重量份作為鏈轉移劑的正辛硫醇，將該些混 合攪拌來準備單體混合液。另外’添加300重量份的離子 交換水、3. 65重量份作為界面活性劑的花王（股）製造的 烷基苯磺酸鈉G-15 ’接著向其中添加上述單體混合液，使 用回流管、氮氣流下的燒瓶，一邊攪拌一邊保持在6〇〇c， 然後添加0.03重直伤作為自由基聚合起始劑的過硫酸 鉀，進行4小時乳化聚合，最後升溫至90°c，使聚合反應 結束。 27 201201384 此處所得的波長轉換用螢光材料成為一次粒徑為1〇〇 =左右的粒子狀’以異丙醇等適當進行後處理，將其過遽 分離’並錢，適當進行H，從而獲雜子狀的波長轉 換用螢光材料（球狀螢光體）。 〈波長轉換用樹脂組成物的製備〉 將1〇〇重昼份作為透明分散介質樹脂的Tosoh (股） 製造的乙稀-乙酸乙烯酯樹脂（EVA):NM3〇pw、1.5重 量份的Arkema Yoshitomi (股）製造的過氧化物熱自由基 聚合起始劑（本實例中，亦作為交聯劑而發揮作用）：S 26 201201384 In the manual. [Examples] However, the present invention will be described in more detail below by way of examples, and is not limited to the examples. [Example 1] <Synthesis of Fluorescent Substance> 200 mg &amp; 4,4,4-tridun + (.sepenoyl H,3_butyl succinyl) was dissolved in 7 ml of ethanol and added thereto. 1 Dissolve sodium hydroformide M ml in Laos. Add 6.2 ^^ of 1,10-morpholine dissolved in 7 ml of ethanol to the previous mixed solution. After stirring for 1 hour, add £11 containing 10311^. (: 13.11112〇 of the aqueous solution of 3.51111, a precipitate was obtained. The precipitate was separated by 'cleaning with ethanol' and dried to obtain a crab light substance Eu(TTA)3Phen. <Swivel for wavelength conversion (spherical fluorescence) Preparation of body> 0.3 parts by weight of the above-obtained Eu(TTA)3Phen as a fluorescent substance, 60 parts by weight of methyl methacrylate as a vinyl compound, and 0.012 parts by weight of n-octyl sulfide as a chain transfer agent Alcohol, the mixture was stirred and mixed to prepare a monomer mixture. Further, '300 parts by weight of ion-exchanged water, 3.6 parts by weight of sodium alkane sulfonate G-15 manufactured by Kao (share) as a surfactant 'Then, the above monomer mixture was added thereto, and a reflux tube and a flask under a nitrogen flow were used. While stirring, the mixture was kept at 6 ° C, and then 0.03 weight of potassium persulfate as a radical polymerization initiator was added, and the emulsion polymerization was carried out for 4 hours, and finally the temperature was raised to 90 ° C to complete the polymerization reaction. 27 201201384 The fluorescent material for wavelength conversion is a particle shape having a primary particle diameter of about 1 〇〇 = 'after appropriate treatment with isopropanol or the like, and the mixture is subjected to excessive enthalpy separation, and H is appropriately obtained to obtain a heterosis. Fluorescent material for wavelength conversion (spherical phosphor). <Preparation of resin composition for wavelength conversion> Ethylene-vinyl acetate resin manufactured by Tosoh Co., Ltd., which is a transparent dispersion medium resin (EVA): NM3 〇pw, 1.5 parts by weight of a peroxide thermal radical polymerization initiator manufactured by Arkema Yoshitomi Co., Ltd. (in this example, also acts as a crosslinking agent):

Luperox 10卜 0. 5 重量份的 Toray Dow Corning (股）製造 的矽烷偶合劑：SZ6030、以及〇. 〇1重量份[以波長轉換用 螢光材料（球狀螢光體）的形態添加；關於螢光物質，波 長轉換用螢光材料1重量份相當於〇〇〇5重量份]的螢光物 質，以9(TC的輥磨機進行混練，從而獲得波長轉換用樹脂 組成物。 〈不含螢光物質的第一封裝片材的製作〉 除了於上述波長轉換用樹脂組成物的製備中，不添加 波長轉換用螢光材料（球狀螢光體）以外，以相同的方式 製備樹脂組成物。將約6 g的該樹脂組成物夾持於脫模片 材中，使用不鏽鋼製間隔片，利用將熱板調整為9〇。〇的壓 製機，以約328 μιη的厚度製作不含螢光物質的第一封裝 片材。 〈含有螢光物質的第二封裝片材的製作〉 除了對上述所得的波長轉換用樹脂組成物，改變間隔Luperox 10 0.25 parts by weight of a decane coupling agent manufactured by Toray Dow Corning Co., Ltd.: SZ6030, and 〇. 1 part by weight [added as a fluorescent material for wavelength conversion (spherical phosphor); A fluorescent substance, a fluorescent material corresponding to 5 parts by weight of fluorene for a wavelength conversion fluorescent material, and a kneading machine of 9 (TC) were used to obtain a resin composition for wavelength conversion. [Preparation of the first encapsulating sheet of the fluorescent material] In the preparation of the above-described resin composition for wavelength conversion, the resin composition was prepared in the same manner except that the wavelength conversion fluorescent material (spherical phosphor) was not added. About 6 g of the resin composition was placed in a release sheet, and a stainless steel spacer was used, and the hot plate was adjusted to a thickness of about 328 μm by using a press machine adjusted to a thickness of about 328 μm. The first encapsulating sheet of the substance. <Preparation of the second encapsulating sheet containing the fluorescent substance> In addition to the resin composition for wavelength conversion obtained as described above, the interval is changed.

S 28S 28

201201384 ^ L ^的厚度以外，以與上述第—封^材的製作相同的方 ^以約272 μιη的厚度獲得含有螢光物質的第二封裝片 〈波長轉換型光電電池封裝材料的製作〉 :上述第-封裝諸與第二封裝片材純於脫模片材 ，吏用不細製間隔 &gt;；’湘將熱板調整為航的壓 機’獲％· 2層結構的波長轉換型光電電池封裝材料。所 的波長轉換型光電電池封裝材料的厚度為6〇() pm。 〈背面用光電電池封裝片材的製作〉 除了與上述第-封裝片材為相同的組成且以厚度 600 μιη的方式調節以外，以相同的方法製作背面用 電池封裝片材。 电 〈波長轉換型光電電池模組的製作〉 於作為保護玻璃的強化玻璃（AsahiGlass (股）製造） 上，以不含波長轉換用螢光材料（球狀螢光體）的第一封 裝片材與強化玻璃接觸的方式載置上述波長轉換型光電電 池封裝材料，然後於其上載置以將電動勢取出至外部的方 式形成的光電電池單元上，進而載置光電電池封裝 片材、以及作為背膜的PET膜（東洋紡（股）製造，商^ 名：A-4300)，使用光電電池用真空加壓層壓機（（股）Npc， LM-50x50-S)，以熱板15(rc、真空1〇分鐘、加壓15分鐘 的條件進行層壓，來製作實例丨的光電電池模組。 此外，所謂以將上述電動勢取出至外部的方式製成的 光電電池單兀’是指使用日立化成工業（股）製造的光電 29 201201384 電池用導電膜CF-105，利用專用的壓接裝置來連接表2 根、背2根的標記線（厚度0.14 mm，寬度2 mm，鍍有 鋅的標記線）’進而將該些表背分別使用橫標記線（日立電 線（股）製造’ A-TPS 0·23χ6.0)料外部取出線的光電 電池單元。另外，對於以將電動勢取出至外部的方式製成 的光電電池單元，是在模組化之前，使用Wac〇m Electric (股）製造的太陽模擬器WXS-155S-10、AM15G、英弘 精機（股）製造的太陽模擬器用;t_v曲線描繪儀Mp_丨6〇， ，獲得光電電池I-V特性。js c (短路電流密度）是將依據 JIS-C-8914測定所得的值作為Jsc (單元）。 [實例2] 〈2層結構的波長轉換型光電電池職材料的製作 作中除中的第一封襄片材、第二封裝片材的 同的古為如表1所示的方式加以變更以外，以 °作實例2的波長轉翻光電電池封裝材料。 、《波長轉換型光電電池模組的製作〉 換型Μ:::製：的波長彳 電池模組。 料作實例2的波長轉換型光; [比較例1、比較例2] :了 2構的波長轉換型光電電池封裝材料的製作， 為如表的第二封裝片材的製作中，以厚度: 較例1及^㈠的方式讀更以外，以相同的方式製作1 乂列2的波長轉換型光電電池封裝材料。In addition to the thickness of L01, a second encapsulating sheet containing a fluorescent material (manufacture of a wavelength conversion type photovoltaic cell encapsulating material) was obtained in the same manner as in the above-described first sealing material at a thickness of about 272 μm. The first-package and the second package sheet are pure to the release sheet, and the spacing is not fine; the 'the hot plate is adjusted to the aeronautical press' to obtain a wavelength-converted photoelectric with a 2-layer structure Battery packaging material. The thickness of the wavelength conversion type photovoltaic cell encapsulating material is 6 〇 () pm. <Preparation of photovoltaic cell encapsulating sheet for back surface> A battery package sheet for a back surface was produced in the same manner except that the composition was the same as that of the above-mentioned first-package sheet and adjusted to a thickness of 600 μm. [Production of a wavelength-converting photovoltaic cell module] On a tempered glass (manufactured by Asahi Glass), which is a cover glass, a first package sheet containing no wavelength conversion fluorescent material (spherical phosphor) The above-mentioned wavelength conversion type photovoltaic cell encapsulating material is placed in contact with the tempered glass, and then placed on the photovoltaic cell unit formed to take the electromotive force to the outside, and further, the photovoltaic cell encapsulating sheet and the back film are placed thereon. PET film (manufactured by Toyobo Co., Ltd., trade name: A-4300), vacuum press laminator for photovoltaic cells (Npc, LM-50x50-S), hot plate 15 (rc, vacuum) The photovoltaic cell module of Example 丨 was fabricated by laminating for 1 minute and under pressure for 15 minutes. In addition, the photovoltaic cell unit made by extracting the above-described electromotive force to the outside means using Hitachi Chemical Industry Co., Ltd. Photoelectric 29 manufactured by the company (2012) The conductive film CF-105 for batteries is connected to the marking lines of the roots and back of the table 2 by a special crimping device (thickness 0.14 mm, width 2 mm, zinc-plated mark) ' Further, the photovoltaic cells of the external take-out line are manufactured by using the horizontal marking line (Hitachi Electric Wire Co., Ltd.) to manufacture the externally taken-out wire. In addition, the method of taking the electromotive force to the outside is performed. The fabricated photovoltaic cell unit is a solar simulator manufactured by Wac〇m Electric (the solar simulators WXS-155S-10, AM15G, and Yinghong Seiki) before the modularization; t_v curve plotter Mp_丨6〇, , obtains the IV characteristic of the photovoltaic cell. js c (short-circuit current density) is a value measured according to JIS-C-8914 as Jsc (cell). [Example 2] <Wavelength conversion type of 2-layer structure In the production of photovoltaic cell materials, the same first and second encapsulating sheets were changed in the same manner as shown in Table 1, and the wavelength was turned over as a photoelectric cell of Example 2. Packaging material. "Manufacture of wavelength conversion type photovoltaic cell module" Change type:::: Wavelength 彳 battery module: The wavelength conversion type light of Example 2; [Comparative Example 1, Comparative Example 2]: The fabrication of a two-layer wavelength conversion type photovoltaic cell packaging material In the production of the second encapsulating sheet as shown in the table, a wavelength conversion type photovoltaic cell encapsulating material of 1 column 2 was produced in the same manner as in the case of reading in the thicknesses of Examples 1 and (1).

S 30 1 1201201384 〈波長轉換型光電電池模組的製作〉 於作為保護玻璃的強化玻璃（Asahi Glass (股）製造） 上载置上述比較例1或比較例2的波長轉換型光電電池 1裝材料，接著於其上載置以將電動勢取出至外部的方式 氣成的光電電池單元上，進而載置背面用光電電池封裝片 材、以及作為背膜的PET膜（東洋紡（股）製造，商品名： A~4300) ’使用光電電池用真空加壓層壓機（（股）NPC， LM-50x50-S)，以熱板15〇°〇、真空1〇分鐘、加壓15分鐘 的條件進行層壓’從而製作比較例1及比較例2的光電電 池模組。 [光電電池模組的評價] 對上述所製作的波長轉換型光電電池模組，使用 Wacom Electric (股）製太陽模擬器 WXS_155S_1〇、 AM1.5G、英仏精機（股）製造的太陽模擬器用I-V曲線描 输儀MP_160，獲得光電電池I-V特性，來作為依據 JIS-C-8914測定而得的Jsc (模組）。AJsc是使用該Jsc (模 組）的值及預先測定的Jsc (單元），利用下述式來算出。 △Jsc = Jsc (模組）_jsc (單元） 將所得的結果歸納於表1 ’將含有波長轉換用螢光材 料（球狀螢光體）的波長轉換型光電電池封裝片材的膜厚 與△ Jsc的關係歸納於圖2中。 [表1] 201201384 分散介質樹脂 中的螢光物質 的含量 第一封裝片材的厚 度（不含螢光物質） 第二封裝片材的厚 度（含有螢光物質） 封裝材 料的總 厚度 △Jsc [重量份1 Tumi [μηι] _ [mA/cm2] 實例1 0.01 —_ U·1 …1 328 272 600 0.536 實例2 U.(J1 600 250 850 0.490 比較例1 成 1 &quot; -J Π Π1 比較例2 ν·ν 1 〇 590 800 590 800 0.462 0.249 0.01 0 “如表1及圖2所示，證實如下情況：若為包含含有螢 光物質的層與不含螢光物質的層的波長轉換型光電電池封 裝材料，則即便含有營光物質的片材的膜厚為300 μηι以 下，亦與波長轉換型光電電池封裝材料包含含有螢光物質 的1層且其膜厚為590 μηι的片材相比，更具有波長轉換 效果。即可知，螢光物質的使用量被抑制在—半以下，且 轉換效率提高。 [實例3] 〈波長轉換用螢光材料（球狀螢光體）2的製備〉 分別量取0. 05 g上述所得的螢光物質 Eu(TTA)3Phen、95 g的甲基丙烯酸甲酯、5 g的乙二醇二 甲基丙烯酸酯、〇·5 g作為熱自由基起始劑的2,2，一偶氮雙 (2, 4-二甲基戊腈），放入2〇〇 mi螺旋管中，使用超音波 清洗器與混合轉子進行攪拌混合。向安裝有冷卻管的可分 離式燒瓶t添加500 g的離子交換水、59.丨g作為界面活 性劑的聚乙烯基醇1. 69%溶液，加以擾拌。接著;其中添 加預先製備的甲基丙烯酸甲酯與乙二醇二甲基丙‘酸酯的、 渑合液，將其一邊以350 ipm攪拌，一邊加熱至5〇它，反S 30 1 1201201384 <Preparation of a wavelength conversion type photovoltaic cell module> The wavelength conversion type photovoltaic cell 1 of Comparative Example 1 or Comparative Example 2 is placed on a tempered glass (manufactured by Asahi Glass) as a cover glass. Then, a photovoltaic cell in which the electromotive force is taken out to the outside is placed thereon, and a photovoltaic cell encapsulating sheet for the back surface and a PET film as a back film are placed thereon (manufactured by Toyobo Co., Ltd., trade name: A ~4300) 'Using a vacuum press laminator for photovoltaic cells (NPC, LM-50x50-S), laminating under the conditions of a hot plate of 15 ° C, vacuum for 1 min, and pressurization for 15 minutes' Thus, the photovoltaic cell modules of Comparative Example 1 and Comparative Example 2 were produced. [Evaluation of Photovoltaic Cell Module] For the wavelength conversion type photovoltaic cell module produced above, the solar simulator for the Sun Simulator manufactured by Wacom Electric (WQS_155S_1〇, AM1.5G, and Infineon) was used. The curve scanner MP_160 obtained the photovoltaic cell IV characteristics as a Jsc (module) measured in accordance with JIS-C-8914. AJsc is calculated using the following formula using the value of the Jsc (module group) and the Jsc (unit) measured in advance. ΔJsc = Jsc (module)_jsc (unit) The results obtained are summarized in Table 1 'Thickness and Δ of the wavelength conversion type photovoltaic cell encapsulating sheet containing the wavelength conversion fluorescent material (spherical phosphor) The relationship of Jsc is summarized in Figure 2. [Table 1] 201201384 Content of fluorescent substance in dispersion medium resin Thickness of first encapsulating sheet (excluding fluorescent substance) Thickness of second encapsulating sheet (containing fluorescent substance) Total thickness of packaging material ΔJsc [ Parts by weight 1 Tumi [μηι] _ [mA/cm2] Example 1 0.01 - _ U · 1 ... 1 328 272 600 0.536 Example 2 U. (J1 600 250 850 0.490 Comparative Example 1 into 1 &quot; -J Π Π 1 Comparative Example 2 ν·ν 1 〇590 800 590 800 0.462 0.249 0.01 0 "As shown in Table 1 and Figure 2, it is confirmed that the wavelength conversion type photoelectric system is a layer containing a layer containing a fluorescent substance and a layer containing no fluorescent substance. In the battery package material, even if the film thickness of the sheet containing the light-emitting material is 300 μm or less, the wavelength conversion type photovoltaic cell encapsulating material includes one sheet containing a fluorescent material and a film thickness of 590 μm. Further, it is known that the amount of the fluorescent substance is suppressed to be less than -half, and the conversion efficiency is improved. [Example 3] <Preparation of Fluorescent Material (Spherical Phosphor) 2 for Wavelength Conversion> 0. 05 g of the above obtained Fluorescent material Eu(TTA)3Phen, 95 g of methyl methacrylate, 5 g of ethylene glycol dimethacrylate, 〇·5 g as a thermal radical initiator 2,2, an azo double (2,4-Dimethylvaleronitrile), placed in a 2〇〇mi spiral tube, stirred and mixed with a mixing rotor using an ultrasonic cleaner. Add 500 g of ions to a separable flask t equipped with a cooling tube The water was exchanged with 59. g of the polyvinyl alcohol as a surfactant, 1.69% solution, and then scrambled. Then, the previously prepared methyl methacrylate and ethylene glycol dimethyl propylene ester were added. , kneading liquid, stirring one side at 350 ipm, heating it to 5 〇, reverse

S 32 201201384 應4小時。對該懸浮液使用Beckman Coulter公司製造的 Beckman Coulter LS13320 (高分解能力型雷射繞射散射法 粒度分布測定裝置），來測定粒徑，結果體積平均徑為104 μιη。然後將沈澱物過濾分離，以離子交換水清洗，於6〇°C 下乾燥，從而獲得藉由懸浮聚合的波長轉換用螢光材料（球 狀螢光體）2。 〈波長轉換用樹脂組成物2的製備〉 將100重量份作為透明分散介質樹脂的Tosoh (股） 製造的乙烯-乙酸乙烯酯樹脂（EVA) : NM30PW、1. 5重 量份的Arkema Yoshitomi (股）製造的過氧化物熱自由基 聚合起始劑（本實例中，亦作為交聯劑而發揮作用）：S 32 201201384 should be 4 hours. The suspension was subjected to Beckman Coulter LS13320 (high resolution-capable laser diffraction scattering particle size distribution measuring apparatus) manufactured by Beckman Coulter Co., Ltd. to measure the particle diameter, and as a result, the volume average diameter was 104 μm. Then, the precipitate was separated by filtration, washed with ion-exchanged water, and dried at 6 ° C to obtain a wavelength conversion fluorescent material (spherical phosphor) 2 by suspension polymerization. <Preparation of Resin Composition 2 for Wavelength Conversion> 100 parts by weight of ethylene-vinyl acetate resin (EVA) manufactured by Tosoh Co., Ltd. as a transparent dispersion medium resin: NM30PW, 1.5 parts by weight of Arkema Yoshitomi (share) The peroxide thermal radical polymerization initiator produced (in this example, also acts as a crosslinking agent):

Luperox 1〇1、〇 5 重量份的 Toray Dow Corning (股）製造 的矽烷偶合劑：SZ6030、以及1重量份（關於螢光物質濃 度’波長轉換用螢光材料1重量份相當於0. 0005重量份） 的上述所得的聚合後的波長轉換用螢光材料（球狀螢光體） 2 ’以9(TC的輥磨機混練，從而獲得波長轉換用樹脂組成 物2。 〈2層結構的波長轉換型光電電池封裝材料的製作〉 除了於實例1中的第一封裝片材的製作中，變更為上 述波長轉換用樹脂組成物2以外，以相同的方式製作實例 3的波長轉換型光電電池封裝材料。 〈波長轉換型光電電池模組的製作〉 以與實例1相同之方式，但改為上述實例3的波長轉 換型光電電池封裝材料，來製作實例3的波長轉換型光電 33 201201384 電池模組。 [光電電池模紐的評價] 利用上述方法來進行實例3的波長轉換型光電電池 組的5平價，結果可知，為Q 73 mA/em2，與實例、 比轉換效率更優異。 、 相 雖然本發明已以較佳實施例揭露如上，然其並非用以 限定本發明，任何熟習此技藝者，在不脫離本發明之精神 和範圍内，當可作些許之更動與潤飾，因此本發明之保護 範圍當視後附之申請專利範圍所界定者為準。 【圖式簡單說明】 圖1是表示本發明的光電電池模組的概略剖面圖。 圖2是表示實例及比較例中獲得的波長轉換型光電電 池封裝材料的膜厚與AJsc的關係的圖表。 【主要元件符號說明】 10 :光電電池單元 20 :保護玻璃 30 :波長轉換塑光電電池封裝材料 32 :第一封裝層 34 :第二封裝層 36 :背面用封裝材料 40 =背膜Luperox 1〇1, 〇5 parts by weight of a decane coupling agent manufactured by Toray Dow Corning Co., Ltd.: SZ6030, and 1 part by weight (about 0.5 parts by weight of the phosphorescent material for wavelength conversion phosphorescent material equivalent to 0.0005 weight) (Partition) The wavelength conversion resin composition 2 obtained by kneading the fluorescent material (spherical phosphor) 2' obtained by the above-mentioned polymerization after the polymerization is obtained by a roll mill of TC. The wavelength of the two-layer structure is obtained. Production of Conversion Photovoltaic Cell Encapsulating Material> In addition to the above-described composition for converting the first encapsulating sheet in Example 1, the wavelength conversion type photovoltaic cell package of Example 3 was produced in the same manner. [Production of Wavelength Conversion Photovoltaic Cell Module] In the same manner as in Example 1, but instead of the wavelength conversion type photovoltaic cell encapsulating material of the above Example 3, the wavelength conversion type photovoltaic 33 201201384 battery module of Example 3 was fabricated. [Evaluation of Photoelectric Cell Modules] Using the above method, the 5 parity of the wavelength conversion type photovoltaic cell of Example 3 was carried out, and as a result, it was found that Q 73 mA/em2, and examples, The invention is more excellent than the conversion efficiency. The present invention has been disclosed in the above preferred embodiments, but it is not intended to limit the invention, and those skilled in the art can make some changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a photovoltaic cell module of the present invention. A graph showing the relationship between the film thickness of the wavelength conversion type photovoltaic cell encapsulating material obtained in the examples and the comparative examples and AJsc. [Description of main components] 10: Photovoltaic cell 20: Protective glass 30: Wavelength-converting plastic photovoltaic cell encapsulating material 32 : First encapsulation layer 34 : second encapsulation layer 36 : encapsulation material for back surface 40 = back film

S 34S 34

Claims (1)

2012013841 七、申請專利範圍： 1. 一種波長轉換型光電電池封裝材料，包括不含螢 光物質的第一封裝層以及含有螢光物質的第二封裝層。 2. 如申請專利範圍第1項所述之波長轉換型光電電 池封裝材料，其中上述螢光物質為銪錯合物。 3. 如申請專利範圍第1項所述之波長轉換型光電電 池封裝材料’其中上述螢光物質内包於以乙烯基化合物作 為單體化合物的樹脂粒子中。 4. 一種光電電池模組，包括光電電池單元以及 設置於上述光電電池單元的受光面側的如申請專 ，第1項至第3項巾任-項所述之波長轉換型光電電 352012013841 VII. Patent application scope: 1. A wavelength conversion type photovoltaic cell packaging material, comprising a first encapsulation layer containing no fluorescent substance and a second encapsulation layer containing a fluorescent substance. 2. The wavelength conversion type photovoltaic cell encapsulating material according to claim 1, wherein the fluorescent substance is a ruthenium complex. 3. The wavelength conversion type photovoltaic cell encapsulating material as described in claim 1, wherein the fluorescent material is contained in a resin particle having a vinyl compound as a monomer compound. 4. A photovoltaic cell module comprising a photovoltaic cell unit and a wavelength conversion type photovoltaic device as set forth in the application specification, item 1 to item 3 of the light-receiving surface side of the photovoltaic cell unit.
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